Novel spiroorthocarbonates

ABSTRACT

Photopolymerizable compositions are provided which are the reaction products of a vinyl ether, a photoinitiator system comprising an iodonium salt, a visible light sensitizer, and an electron donor compound. These monomeric/oligomeric compositions may also include epoxides, polyols, spiroorthocarbonates. One embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, a spiroorthocarbonate, and a photoinitiator system. Another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, and a photoinitiator system. Still another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, a spiroorthocarbonate, and a photoinitiator system.  
     Still further, another embodiment of the present invention is certain novel spiroorthocarbonate compounds. Each of these novel spiroorthocarbonate compounds include at least one epoxy group as a substituent.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] The government has certain rights in this invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] Not applicable.

FIELD OF THE INVENTION

[0003] This invention relates in general to compositions of matter and,more particularly, to compositions that include a vinyl ether and aphotoinitiator system. These compositions may also include an epoxide, apolyol, and/or a spiroorthocarbonate (SOC), which may be one of thenovel spiroorthocarbonates disclosed herein. The polymerizablecompositions of the present invention are useful for a variety ofapplications, including for use as dental materials such as adhesivesand composites.

BACKGROUND OF THE INVENTION

[0004] Many types of monomers undergo shrinkage during polymerization toa degree that makes them generally unsuited for use in numerousapplications, including for use as stress-free composites, high-strengthadhesives, and precision castings. As an example, when such monomers areused in composites which contain inorganic fillers, the polymeric matrixis subject to failure when the polymer shrinks and pulls away from thefiller particles. Failure of the composite can also occur when thematrix ruptures as a result of voids or micro cracks which form in thematrix during polymerization shrinkage.

[0005] Polymeric matrices commonly employed in dental materials such asadhesives and composites are based on2,2′-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)]phenyl propane (BisGMA).A significant problem associated with the use of this monomer in dentalapplications is the shrinkage which occurs as the monomer ispolymerized. The BisGMA monomer itself typically experiences highshrinkage, and when a low viscosity reactive diluent is combined withthe monomer, the shrinkage may even be higher. The adverse effects ofsuch shrinkage are believed to include increased postoperativesensitivity, the formation of marginal gaps between the dentalrestoration and the cavity wall, cracking of the restoration, andmicroleakage and potential failure of the restoration.

[0006] The discovery that spiroorthocarbonates may undergo reducedpolymerization contraction and possibly polymerization expansion has ledto the suggestion of their use in reinforced composites, including asdental materials. Spiroorthocarbonates are esters of orthocarboxylicacid and have four oxygen atoms bonded to a single carbon atom, with thecarbon atom being common to two ring systems. The expansion of thespiroorthocarbonates on polymerization is attributed to a doublespiro-cyclic ring opening of the spiroorthocarbonates, resulting in thebreaking of two covalent bonds to form one new bond.

[0007] Initial attempts to form a homogeneous polymer matrix fromcertain spiroorthocarbonates and BisGMA resin mixtures provedunsuccessful because of the incomplete polymerization of thespiroorthocarbonates. Thompson et al., J. Dental Research 58:15221532(1979). More recent studies demonstrated that homogeneous mixtures ofother spiroorthocarbonates and BisGMA could be obtained. Stansbury, J.Dental Research 70:527; Abstract No. 2088 (1991).

[0008] The photocationic-initiated expansion polymerization of alicyclicspiroorthocarbonate monomers and the potential use of the resultingpolymers in dental materials have been previously reported by some ofthe present inventors, with others. Byerley et al., Dent. Mater.8:345-350 (1992). The specific spiroorthocarbonates identified byByerley et al. include cis/cis, cis/trans, and trans/transconfigurational isomers of2,3,8,9-di(tetramethylene)-1,5,7,11-tetraoxaspiro[5.5]undecane. Thesespiroorthocarbonates were determined to undergo an expansion of 3.5%during homopolymerization and demonstrated acceptable cytotoxicity andgenotoxicity properties, making them promising components of compositeresin matrix materials.

[0009] Some of the present inventors, with others, have also previouslyreported on the preparation of a copolymer of an alicyclicspiroorthocarbonate and an unidentified monofunctional epoxide, with theobservation that there were no indications of the formation of smallring compounds as polymerization by-products. Byerley et al., J. DentalResearch 69:263; Abstract No. 1233 (1990). The copolymerization oftrans/trans-2,3,8,9-di(tetramethylene)-1,5,7,11- tetraoxaspiro[5.5]undecane and commercially available multifunctional epoxides wasalso disclosed in a paper presented by Byerley et al., Abstract No.1233, cited above. However, no physical or mechanical properties,including percentage shrinkage, of the copolymer compositions weredisclosed. Still further, spiroorthocarbonate copolymers have beencreated that are capable of yielding a hard, non-shrinking matrix resin.These copolymers include atrans/trans-2,3,8,9-di(tetramethylene)-1,5,7,11-tetraoxaspiro[5.5]undecanespiroorthocarbonate, a polymerizable epoxy resin, and a hydroxylcontaining material, as described in U.S. Pat. No. 5,808,108.

[0010] A polymeric composition that includes a vinyl ether, a diepoxide,a polyol, and a photoinitiator system including an iodonium salt and avisible light sensitizer has previously been disclosed by one of thepresent inventors. Eick et al., J. Dental Research, 77B:639; AbstractNo. 63 (1998). This photoinitiator system is similar to that disclosedin PCT/US95/14098, but does not utilize an electron donor compound. Thereaction rate for forming this disclosed polymeric composition hassubsequently been determined to be very slow, making the compositiongenerally unsuited for use in applications requiring faster reactionrates.

[0011] An epoxide/polyol polymeric composition that includes aphotoinitiator system comprising an iodonium salt, a visible lightsensitizer, and an electron donor compound is disclosed by one of thepresent inventors, with another, in PCT application Nos. PCT/US98/04458('458 application) and PCT/US98/04029 ('029 application). The '458application further suggests that other cationically polymerizablepolymers, such as vinyl ethers, can be incorporated into theepoxide/polyol polymeric composition. However, this application does notsuggest that vinyl ether may be a substantial component of thecomposition, but only an optional additive.

[0012] The results of an attempted block polymerization of a living poly(spiroorthocarbonate) and a vinyl ether are disclosed by T. Endo et al.in Macromolecules, vol. 21, pp. 1186-1187, in an article entitled“Polymerization and Block Copolymerization Initiated by Unusually StableLiving Propagating Species Formed in the Cationic Polymerization ofSpiro Ortho Carbonate” (1988). The disclosed reactions required heat anda considerable amount of time for polymerization. In addition,homopolymerization of n-butyl vinyl ether was observed. This articledoes not disclose using a ternary photoinitiator system to promotepolymerization.

[0013] A diepoxy spiroorthocarbonate, namely,3,23-dioxatrispiro[tricyclo[3.2.1.0<2,4>]octane-6,5′-1,3-dioxane-2′2″-1,3-dioxane-5″,7′″-tricyclo[3.2.1.0<2,4>octane],is disclosed in a book entitled, “Expanding Monomers, Synthesis,Characterization and Applications,” edited by R. J. Sadhir and R. M.Luck, CRC Press, Boca Raton (1992), pp. 329-332. This compound ispurported to have the following structure:

[0014] The book does not suggest that vinyl ethers may be combined withthis spiroorthocarbonate, and the polymerization of the compound isreported to require extended reaction times and high temperatures (i.e.,1 hr/110° C., 1 hr/125° C., 4 hr/150° C., and 8 hr/150° C.). Thedisclosed polymerizations involved using a cationic initiator, but thereis no suggestion that a visible light photoinitiator system could beused. The extended reaction times, elevated temperatures, and reactionconditions make the disclosed polymerizable composition generallyunsuited for many applications, including use as dental materials.

[0015] Despite the advances resulting from the above-noted polymericcompositions and SOCs, a need still exists for polymerizablecompositions having properties desirable for use as dental materialssuch as adhesives and composites, as well as other applications.

SUMMARY OF THE INVENTION

[0016] In one aspect, the present invention is directed to aphotopolymerizable composition comprising a substantial amount of avinyl ether, and a photoinitiator system that includes an iodonium salt,a visible light sensitizer, and an electron donor compound. Thephotoinitiator system has a photoinduced potential greater than or equalto that of N,N-dimethylaniline in a standard solution of 2.9×10⁻⁵moles/g diphenyl iodonium hexafluoroantimonate and 1.5×10⁻⁵ moles/gcamphorquinone in 2-butanone. The composition of the invention producesa polymerized product by subjecting the composition to conditionssuitable for causing polymerization of the vinyl ether. The compositionmay further include an epoxide, a polyol, and/or one or more compoundsrepresented by formula I below:

[0017] wherein

[0018] R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl or substitutedaryl, or

[0019] R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6;—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2; and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, and R₆ and R₇, provided that

[0020] R₃, R_(4,) R₇, and R₈ are hydrogen when R₁•R₂ and R₅•R₆ areindependently selected from the group consisting of —CH₂(CH₂)_(n)CH₂—where n=3, 4, 5 and 6 so as to form an alicyclic ring between R₁ and R₂and between R₅ and R₆;

[0021] R₂, R₃, R₄, R₆, R₇, and R₈ are hydrogen when R₁ and R₅ areindependently selected from the group consisting of alkyl, aryl,substituted alkyl, and substituted aryl;

[0022] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₆ are independentlyselected from the group consisting of alkyl, aryl, substituted alkyl,and substituted aryl and R₃ and R₇ are independently selected from thegroup consisting of —(CH₂)_(n)—O—(O═C)—R₉ where n=1 and 2 and R₉=H,alkyl, aryl, substituted alkyl or substituted aryl;

[0023] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are independentlyselected from the group consisting of H, alkyl, aryl, substituted alkyl,and substituted aryl and R₆•R₇=—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1,and 2 so as to form an alicyclic ring between R₆ and R₇;

[0024] R₁, R₄, R₅, and R₈ are hydrogen when R₂•R₃ and R₆•R₇ areindependently selected from the group consisting of—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form an alicyclicring between R₂ and R₃ and between R₆ and R₇;

[0025] R₁, R₄, R₅, and R₈ are hydrogen when R₂ is independently selectedfrom the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆, and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl;

[0026] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are independentlyselected from the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl;

[0027] R₃, R₄, R₅, R₆, R₇, and R₈ are independently selected from thegroup consisting of the group consisting of hydrogen, alkyl, aryl,substituted alkyl, and substituted aryl, when R₁•R₂=—O— so as to form anoxirane ring between R₁ and R₂; and

[0028] R₃, R₄, R₇, and R₈ are independently selected from the groupconsisting of hydrogen, alkyl, aryl, substituted alkyl, and substitutedaryl, when R₁•R₂ and R₅•R₆=—O— so as to form an oxirane ring between R₁and R₂ and between R₅ and R₆. As used herein, alkyl refers to groupshaving 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and morepreferably 1 to 8 carbon atoms. The term “SOC” is used herein to referto spiroorthocarbonates. When a spiroorthocarbonate is used in thepolymerizable composition, the composition is particular useful as adental material such as an adhesive or a composite, with the reactionproduct forming a matrix in which nonreactive dental fillers may bedispersed.

[0029] Another aspect of the present invention is directed to certainnovel spiroorthocarbonates of formula (I) that contain epoxy groups.Namely, the invention includes the compounds5,5-diethyl-19-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′4″-bicyclo[4.1.0]heptane](DECHE),7,26-dioxatrispiro[bicyclo[4.1.0]heptane-4,5′-1,3-dioxane-2′2″-1,3-dioxane-5″,4″-bicyclo[4.1.0]heptane](DCHE),5-5-diethyl-18-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′3″-bicyclo[3.1.0]hexane](DECPE),6,24-dioxatrispiro[bicyclo[3.1.0]hexane-3,5′-1,3-dioxane-2′2″-1,3-dioxane-5″3′″-bicyclo[3.1.0]hexane](DCPE),3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[4.1.0]hept-3-yl)methyl]spiro [5.5]undecane, 3,9-bis[7-oxabicyclo[4.1.0]hept-3-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[4.1.0]hept-2-yl)methyl]spiro[5.5]undecane,3,9-bis[7-oxabicyclo[4.1.0]hept-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis[6-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane,3,9-bis[6-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,9-bis[7-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis[7-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane,2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],5,12-diemthyl-2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],4,5,5,11-tetramethyl-8,10-13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],and 1,5,7,11-tetraoxaspiro[5.5]undecane.

BRIEF DESCRIPTION OF THE DRAWING

[0030] In the accompanying drawing which forms a part of thespecification and is to be read in conjunction therewith:

[0031]FIG. 1 is a graph showing the effect of an electron donor compoundon the photohomopolymerization of vinyl ethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] One aspect of the present invention is directed to apolymerizable composition comprising one or more vinyl ethers (VE) and aternary photoinitiator system. The composition results in a polymerizedproduct when the one or more vinyl ethers are contacted with the ternaryphotoinitiator system under conditions sufficient to promotepolymerization of the vinyl ether. The polymerizable composition mayalso include an epoxy compound, an optional polyol, and an optionalspiroorthocarbonate (SOC). Preferably, when an epoxy compound isincluded in the vinyl ether-based composition of the present invention,a polyol is also included as part of the composition. However, this neednot be the case, and an epoxy compound may be included when a polyol isnot included. In another embodiment, the polymerizable compositionincludes vinyl ether, an SOC, and the ternary photoinitiator system. Ina further embodiment, the polymerizable composition includes vinylether, an epoxy compound, a polyol and the ternary photoinitiatorsystem. Still another embodiment of the present invention is apolymerizable composition that includes vinyl ether, an SOC, an epoxycompound, a polyol and the ternary photoinitiator system.

[0033] Any cationically reactive vinyl ether may be used inpolymerizable compositions of the present invention. Examples of vinylethers that may be used include, but are not limited to, tri(ethyleneglycol) divinyl ether (TEGDVE), glycidyl vinyl ether (GVE), butanediolvinyl ether (BDVE), di(ethylene glycol) divinyl ether (DEGDVE),1,4-cyclohexanedimethanol divinyl ether (CHDMDVE),4-(1-propenyloxymethyl)-1,3-dioxolan-2-one (POMDO), 2-chloroethyl vinylether (CEVE), or 2-ethylhexyl vinyl ether (EHVE), ethyl vinyl ether(EVE), n-propyl vinyl ether (NPVE), isopropyl vinyl ether (IPVE),n-butyl vinyl ether (NBVE), isobutyl vinyl ether (IBVE), octadecyl vinylether (ODVE), cyclohexyl vinyl ether (CVE), butanediol divinyl ether(BDDVE), hydroxybutyl vinyl ether (HBVE), cyclohexanedimethanolmonovinyl ether (CHMVE), tert-butyl vinyl ether (TBVE), tert-amyl vinylether (TAVE), dodecyl vinyl ether (DDVE), ethylene glycol divinyl ether(EGDVE), ethylene glycol monovinyl ether (EGMVE), hexanediol divinylether (HDDVE), hexanediol monovinyl ether (HDMVE), diethylene glycolmonovinyl ether (MVE-2), triethyleneglycol methyl vinyl ether (MTGVE),tetraethylene glycol divinyl ether (DVE-4), trimethylolpropane trivinylether (TMPTVE), aminopropyl vinyl ether (APVE), poly-tetrahydrofurandivinyl ether (PTHFDVE), pluriol-E200 divinyl ether (PEG200-DVE),n-butyl vinyl ether (n-BVE), 4-hydroxybutylvinylether (HBVE), ethyleneglycol butyl vinyl ether (EGBVE), 2-diethylaminoethyl vinyl ether(DEAEVE), dipropropylene glycol divinyl ether (DPGDVE), octadecyl vinylether (ODVE), a vinyl ether terminated aromatic ester monomer (i.e.,hydroxybutyl vinyl ether isophthalate which can be purchased fromAllied-Signal Inc., Engineered Materials Sector, P.O. Box 2332R,Morristown, N.J. 07962 under the trademark VECTOMER 4010), a vinyl etherterminated aliphatic ester monomer (i.e., cyclohexane dimethanolmonovinyl ether glutarate which can be purchased from Allied-Signal Inc.under the trademark VECTOMER 4020), a vinyl ether terminated aliphaticurethane oligomer (i.e., VECTOMER 2020 which can be purposed fromAllied-Signal Inc.), and a vinyl ether terminated aromatic urethaneoligomer (i.e., VECTOMER 2015 and VECTOMER 2010, both of which can bepurchased from Allied Signal Inc.).

[0034] The ternary photoinitiator system used in the polymerizablecompositions of the present invention allows efficient cationicpolymerization under conditions of room temperature and standardpressure. In addition, the initiator system can, under appropriateconditions, initiate both cationic and free-radical polymerization. Thisproperty permits its use with a variety of photopolymerizablecompositions. Use of the initiator systems of the invention can providea substantial reduction in the time required for the presentcompositions to cure to a tack-free gel or solid. This reduction in geltime can in some cases represent about a 30 to 70% decrease in the timerequired for a resin composition to harden to a tack-free gel or solid.Some systems fail to polymerize altogether in the absence of an electrondonor.

[0035] The first component of the ternary photoinitiator system is aniodonium salt (PI), i.e., a diaryliodonium salt. The iodonium saltshould be soluble in a monomer used to make the composition andpreferably is shelf-stable, meaning it does not spontaneously promotepolymerization when dissolved therein in the presence of the sensitizerand the electron donor compound, the second and third components of thephotoinitiator system. Accordingly, selection of a particular iodoniumsalt may depend to some extent upon the particular monomer, sensitizerand donor chosen. Suitable iodonium salts are described in U.S. Pat.Nos. 3,729,313; 3,741,769; 3,808,006; 4,250,053 and 4,394,403, theiodonium salt disclosures of which are incorporated herein by reference.The iodonium salt can be a simple salt, containing an anion such as Cl⁻,B⁻, I⁻ or C₆H₅SO₃ ⁻; or a metal complex salt containing an antimonate,arsenate, phosphate or borate such as SbF₅OH⁻ or AsF₆ ⁻. Mixtures ofiodonium salts can be used if desired.

[0036] Aromatic iodonium complex salts of the structure below may beused as one of the components of the ternary photoinitiator system:

[0037] wherein

[0038] Ar¹ and Ar² are aromatic groups having 4 to 20 carbon atoms andare selected from the group consisting of phenyl, thienyl, furanyl andpyrazolyl groups;

[0039] Z is selected from the group consisting of oxygen; sulfur;

[0040] wherein R is aryl (of 6 to 20 carbons, such as phenyl) or acyl(of 2 to 20 carbons, such as acetyl, benzoyl, and the like); acarbon-to-carbon bond; or

[0041] wherein R₁ and R₂ are selected from hydrogen, alkyl radicals of 1to 4 carbons, and alkenyl radicals of 2 to 4 carbons;

[0042] n is zero or 1; and

[0043] X is a halogen-containing complex anion selected from the groupconsisting of tetrafluoroborate, hexafluorophosphate,hexafluoroarsenate, and hexafluoroantimonate.

[0044] The aromatic iodonium cations are stable and are well known andrecognized in the art. See for example, U.S. Pat. Nos. 3,565,906;3,712,920; 3,759,989; and 3,763,187; F. Beringer, et al., DiaryliodoniumSalts IX, J. Am. Chem. Soc. 81,342-51 (1959) and F. Beringer, et al.,Diaryliodonium Salts XXIII, J. Chem. Soc. 1964, 442-51; F. Beringer, etal., Iodonium Salts Containing Heterocyclic Iodine, J. Org. Chem. 30,1141-8 (1965); J. Crivello et al., Photoinitiated CationicPolymerization with Triarylsulfonium Salts, J. Polymer Science, 17, 977(1979).

[0045] Representative Ar¹ and A² groups are aromatic groups having 4 to20 carbon atoms selected from phenyl, thienyl, furanyl, and pyrazolylgroups. These aromatic groups may optionally have one or more fusedbenzo rings (e.g., naphthyl and the like; benzothienyl; dibenzothienyl;benzofuranyl, dibenzofuranyl; and the like). Such aromatic groups mayalso be substituted, if desired, by one or more of the followingnon-basic groups which are essentially non-reactive with epoxide andhydroxy: halogen, nitro, N-arylanilino groups, ester groups (e.g.,alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl,phenoxycarbonyl), sulfo ester groups (e.g., alkoxylsulfonyl such asmethoxysulfonyl and butoxysulfonyl, phenoxysulfonyl, and the like),amido groups (e.g., acetamido, butyramido, ethylsulfonamido, and thelike), carbamyl groups (e.g., carbamyl, N-alkylcarbamyl,N-phenylcarbamyl, and the like), sulfamyl groups (e.g., sulfamyl,N-alkylsulfamyl, N,N-dialkylsulfamyl, N-phenylsulfamyl, and the like),alkoxy groups (e.g., methoxy, ethoxy, butoxy, and the like), aryl groups(e.g., phenyl), alkyl groups (e.g., methyl, ethyl, butyl, and the like),aryloxy groups (e.g., phenoxy) alkylsulfonyl (e.g., methylsulfonyl,ethylsulfonyl, and the like), arylsulfonyl groups (e.g., phenylsulfonylgroups), perfluoroalkyl groups (e.g., trifluoromethyl, perfluoroethyl,and the like), and perfluoroalkylsulfonyl groups (e.g.,trifluoromethylsulfonyl, perfluorobutylsulfonyl, and the like).

[0046] Examples of useful aromatic iodonium complex salt photoinitiatorsinclude: diphenyliodonium tetrafluoroborate; di(4-methylphenyl)iodoniumtetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate;di(4-heptylphenyl)iodonium tetrafluoroborate; di(3-nitrophenyl)iodoniumhexafluorophosphate; di(4-chlorophenyl)iodonium hexafluorophosphate;di(naphthyl)iodonium tetrafluoroborate;di(4-trifluoromethylphenyl)iodonium tetrafluoroborate; diphenyliodoniumhexafluorophosphate; di(4-methylphenyl)iodonium hexafluorophosphate;diphenyliodonium hexafluoroarsenate; di(4-phenoxyphenyl)iodoniumtetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate;3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate;diphenyliodonium hexafluoroantimonate; 2,2′-diphenyliodoniumtetrafluoroborate; di(2,4-dichlorophenyl)iodonium hexafluorophosphate;di(4-bromophenyl)iodonium hexafluorophosphate;di(4-methoxyphenyl)iodonium hexafluorophosphate;di(3-carboxyphenyl)iodonium hexafluorophosphate;di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate;di(3-methoxysulfonylphenyl)iodonium hexafluorophosphate;di(4-acetamidophenyl)iodonium hexafluorophosphate;di(2-benzothienyl)iodonium hexafluorophosphate; (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate; diphenyliodoniumhexafluoroantimonate; [4-(2-hydroxytetradecyloxyphenyl)]phenyliodoniumhexafluoroantimonate (CD 1012); and [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium tetrakis (pentafluorophenyl)borate (RHO 2074).

[0047] Of the aromatic iodonium complex salts which are suitable for usein the compositions of the invention, diaryliodonium hexafluorophosphateand diaryliodonium hexafluoroantimonate are among the preferred salts.Specific examples of such salts are (4-octyloxyphenyl) phenyliodoniumhexafluoroantimonate (OPIA),[4-(2-hydroxytetradecyloxyphenyl)]phenyliodoniumhexafluoroantimonate,and [4-(1-methylethyl)phenyl] (4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate. These salts are preferred because, ingeneral, they are more thermally stable, promote faster reaction, andare more soluble in inert organic solvents than are other aromaticiodonium salts of complex ions.

[0048] The aromatic iodonium complex salts may be prepared by metathesisof corresponding aromatic iodonium simple salts (such as, for example,diphenyliodonium bisulfate) in accordance with the teachings of Beringeret al., J. Am. Chem. Soc., 81,342 (1959). Thus, for example, the complexsalt diphenyliodonium tetrafluoroborate is prepared by the addition at60° C. of an aqueous solution containing 29.2 g silver fluoroborate, 2 gfluoroboric acid, and 0.5 g phosphorous acid in about 30 ml of water toa solution of 44 g (139 millimoles) of diphenyliodonium chloride. Thesilver halide that precipitates is filtered off and the filtrateconcentrated to yield diphenyliodonium fluoroborate which may bepurified by recrystallization.

[0049] The aromatic iodonium simple salts may be prepared in accordancewith Beringer et al., above, by various methods including: (1) couplingof two aromatic compounds with iodyl sulfate in sulfuric acid, (2)coupling of two aromatic compounds with an iodate in acetic acid-aceticanhydride-sulfuric acid, (3) coupling of two aromatic compounds with aniodine acrylate in the presence of an acid, and (4) condensation of aniodoso compound, an iodoso diacetate, or an iodoxy compound with anotheraromatic compound in the presence of an acid. Diphenyliodonium bisulfateis prepared by method (3), for example, by the addition over a period ofeight hours at below 5° C. of a mixture of 35 ml of conc. sulfuric acidand 50 ml of acetic anhydride to a well-stirred mixture of 55.5 ml ofbenzene, 50 ml of acetic anhydride, and 53.5 g of potassium iodate. Themixture is stirred for an additional four hours at 0°-5° C. and at roomtemperature (about 25° C.) for 48 hours an treated with 300 ml ofdiethyl ether. On concentration, crude diphenyliodonium bisulfateprecipitates and may be purified by recrystallization if desired.

[0050] The second component in the photoinitiator system is thephotosensitizer (PS). Desirably, the photoinitiator should be sensitizedto the visible spectrum to allow the polymerization to be initiated atroom temperature using visible light. The sensitizer should be solublein the photopolymerizable composition, free of functionalities thatwould substantially interfere with the cationic curing process, andcapable of light absorption within the range of wavelengths betweenabout 300 and about 1000 nanometers.

[0051] A sensitizer is selected based in part upon shelf stabilityconsiderations. Accordingly, selection of a particular sensitizer maydepend to some extent upon the particular vinyl ether, other resincomponents, iodonium salt, and electron donor chosen.

[0052] Suitable sensitizers include compounds in the followingcategories: ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes,acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes,aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons,p-substituted aminostyryl ketone compounds, aminotriaryl methanes,merocyanines, squarylium dyes and pyridinium dyes. Ketones (e.g.,monoketones or alpha-diketones), ketocoumarins, aminoarylketones andp-substituted aminostyryl ketone compounds are preferred sensitizers.For applications requiring deep cure (e.g., cure of highly-filledcomposites), it is preferred to employ sensitizers having an extinctioncoefficient below about 1000 lmole⁻¹cm⁻¹, more preferably about or below100 lmole⁻¹cm⁻¹, at the desired wavelength of irradiation forphotopolymerization, or alternatively, the initiator should exhibit adecrease in absorptivity upon light exposure. Many of thealpha-diketones are an example of a class of sensitizers having thisproperty, and are particularly preferred for dental applications.

[0053] By way of example, a preferred class of ketone sensitizers hasthe formula:

ACO(X)_(b)B

[0054] where X is CO or CR₁R² where R¹ and R² can be the same ordifferent, and can be hydrogen, alkyl, alkaryl or aralkyl, b is zero orone, and A and B can be the same or different and can be substituted(having one or more non-interfering substituents) or unsubstituted aryl,alkyl, alkaryl, or aralkyl groups, or together A and B can form a cyclicstructure which can be a substituted or unsubstituted cycloaliphatic,aromatic, heteroaromatic or fused aromatic ring.

[0055] Suitable ketones of the above formula include monoketones (b=0)such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2-pyridyl ketone,di-2-furanyl ketone, di-2-thiophenyl ketone, benzoin, fluorenone,chalcone, Michler's ketone, 2-fluoro-9-fluorenone, 2-chlorothioxanthone,acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene,2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone,n-butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine,3-acetylcoumarin and the like. Suitable diketones includearalkyldiketones such as anthraquinone, phenanthrenequinone, o-, m- andp-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7- and1,8-diacetylnaphthalene, 1,5-, 1,8- and 9,10-diacetylanthracene, and thelike. Suitable α-diketones (b=1 and X=CO) include 2,3-butanedione,2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione,3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzyl, 2,2′-3 3′-and 4,4′-dihydroxylbenzyl, furyl, di-3,3′-indolylethanedione,2,3-bomanedione (camphorquinone), biacetyl, 1,2-cyclohexanedione,1,2-naphthaquinone, acenaphthaquinone, and the like.

[0056] Examples of particularly preferred visible light sensitizersinclude camphorquinone (CQ); 2-chlorothioxanthan-9-one; glyoxal;biacetyl; 3,3,6,6-tetramethylcyclohexanedione;3,3,7,7-tetramethyl-1,2-cycloheptanedione;3,3,8,8-tetramethyl-1,2-cyclooctanedione;3,3,18,18-tetramethyl-1,2-cyclooctadecanedione; dipivaloyl; benzyl;furyl; hydroxybenzyl; 2,3-butanedione; 2,3-pentanedione;2,3-hexanedione; 3,4-hexanedione; 2,3-heptanedione; 3,4-heptanedione;2,3-octanedione; 4,5-octanedione; and 1,2-cyclohexanedione. Mostpreferably, the photosensitizer is (+/−) camphorquinone.

[0057] The third component of the initiator system is one or moreelectron donor compounds (ED). The electron donor compound(s) shouldmeet the requirements set forth below and be soluble in thepolymerizable composition. The donor can also be selected inconsideration of other factors, such as shelf stability and the natureof the polymerizable materials, iodonium salt and sensitizer chosen. Aclass of donor compounds that may be useful in the inventive systems maybe selected from some of the donors described in Palazzotto et al., U.S.Pat. No. 5,545,676. Possible donor compounds that meet the criteria setforth by Palazzotto et al. must then be tested using one or both of themethods set forth below to determine if they will be useful donors forthe photopolymerizable compositions of the invention.

[0058] The donor is typically an alkyl aromatic polyether or an alkyl,aryl amino compound wherein the aryl group is optionally substituted byone or more electron withdrawing groups. Examples of suitable electronwithdrawing groups include carboxylic acid, carboxylic acid ester,ketone, aldehyde, sulfonic acid, sulfonate and nitrile groups.

[0059] The suitability of a compound for use as an electron donor in thecompositions of the invention may be determined by measuring thephotoinduced potential of a sample photoinitiator system that includesthe compound. The photoinduced potential can be evaluated in thefollowing manner. A standard solution is prepared that contains 2.9×10⁻⁵moles/g of diphenyl iodonium hexafluoroantimonate and 1.5×10⁻⁵ moles/gof camphorquinone (CQ) in 2-butanone. A pH electrode is then immersed inthe solution and a pH meter is calibrated to zero mV. A test solution ofthe standard solution and the compound is prepared next using thecompound at a concentration of 2.9×10⁻⁵ moles/g. This test solution isirradiated using blue light having a wavelength of about 400 to 500 nmhaving an intensity of about 200 to 400 mW/cm² for about 5 to 10 secondsat a distance of about 1 mm. Millivolts relative to the standardsolution are then determined by immersing the pH electrode in the testsolution and obtaining a mV reading on the pH meter. Useful donors arethose compounds that provide a reading of at least 50 mV relative to thestandard solution, and preferably provide a gel time for thecompositions that is at least about 30 to 40 percent shorter than forcompositions that do not contain the donor. Higher mV readings aregenerally indicative of greater activity.

[0060] In some instances there may be some uncertainty regarding theoutcome of the above. procedure. This may be due to questions oruncertainty arising from the instrumentation employed, from the way theprocedure was carried out, or other factors, or one may wish to verifythe suitability of a particular compound. A second test may be performedto verify the result obtained by following the above procedure andresolve any such uncertainty.

[0061] The second method involves the evaluation of the photoinducedpotential of an initiator system that includes the compound compared toa system that includes N,N-dimethylaniline. For this method, a standardsolution of 2.9×10⁻⁵ moles/g diphenyl iodonium hexafluoroantimonate,1.5×10⁻⁵ moles/g camphorquinone (CQ) and 2.9×10⁻⁵moles/g ofN,N-dimethylaniline in 2-butanone is prepared. A pH electrode is thenimmersed in the solution and a pH meter is calibrated to zero mV. Thestandard solution is irradiated with blue light having a wavelength ofbetween about 400-500 nm and an intensity of about 200 to 400 mW/cm² forabout 5 to 10 seconds using a focused light source such as a dentalcuring light at a distance of about 1 mm. After light exposure, thepotential of the solution is measured by immersing a pH electrode in theirradiated standard solution and reading the potential in mV using a pHmeter. A test solution is then prepared using 2.9×10⁻⁵moles/g ofdiphenyl iodonium hexafluoroantimonate, 1.5×10⁻⁵ moles/g ofcamphorquinone and 2.9×10⁻⁵moles/g of the compound in 2-butanone. Thetest solution is irradiated and the photoinduced potential measuredusing the same technique as described for the standard solution. If thetest solution has a photoinduced potential that is the same as orgreater than that of the N,N-dimethylaniline containing standardsolution, then the compound is a useful donor.

[0062] A preferred group of alkyl, aryl amine donor compounds isdescribed by the following structural formula:

[0063] wherein

[0064] each R₁ is independently H; C₁₋₁₈ alkyl that is optionallysubstituted by one or more halogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈alkylthio, C₃₋₁₈ cycloalkyl, aryl, COOH, COOC₁₋₁₈ alkyl, (C₁₋₁₈alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, SO₃R²; aryl that is optionally substituted byone or more electron withdrawing groups; or the R¹ groups together mayform a ring,

[0065] where R² is H; C₁₋₁₈ alkyl that is optionally substituted by oneor more halogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈cycloalkyl, aryl, COOH, COOC₁₋₁₈ alkyl, (C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl,or SO₃H; and

[0066] Ar is aryl that is optionally substituted by one or more electronwithdrawing groups. Suitable electron withdrawing groups include —COOH,—COOR², —SO₃R², —CN, —CO—C₁₋₁₈alkyl, and C(O)H groups.

[0067] A preferred group of aryl alkyl polyethers has the followingstructural formula:

[0068] wherein n=1-3, each R₃ is independently H or C₁₋₁₈ alkyl that isoptionally substituted by one or more halogen, —CN, —OH, —SH, C₁₋₁₈alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈ cycloalkyl, aryl, substituted aryl,—COOH, —COOC₁₋₁₈ alkyl, —(C₁₋₁₈ alkyl)₀₋₁—COH, —(C₁₋₁₈alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, —CO—C₁₋₁₈ alkyl, —C(O)H or —C₂₋₁₈ alkenylgroups and each R₄ can be C₁₋₁₈ alkyl that is optionally substituted byone or more halogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈cycloalkyl, aryl, substituted aryl, —COOH, —COOC₁₋₁₈ alkyl, —(C₁₋₁₈alkyl)₀₋₁—COH, —(C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, —CO—C₁₋₁₈ alkyl, —C(O)Hor —C₂₋₁₈ alkenyl groups.

[0069] In each of the above formulas, the alkyl groups can bestraight-chain or branched, and the cycloalkyl group preferably has 3 to6 ring carbon atoms but may have additional alkyl substitutions up tothe specified number of carbon atoms. The aryl groups may be carbocyclicor heterocyclic aryl, but are preferably carbocyclic, and morepreferably are phenyl rings.

[0070] Preferred donor compounds include, but are not limited to,4,4′-bis(diethylamino) benzophenone, 4-dimethylaminobenzoic acid(4-DMABA), ethyl 4-dimethylaminobenzoate (EDMAB), 3-dimethylaminobenzoic acid (3-DMABA), 4-dimethylaminobenzoin (DMAB),4-dimethylaminobenzaldehyde (DMABAL), 1,2,4-trimethoxybenzene (TMB), andN-phenylglycine (NPG).

[0071] The photoinitiator compounds are provided in an amount effectiveto initiate or enhance the rate of cure of the resin system. It has beenfound that the amount of donor that is used can be critical,particularly when the donor is an amine. Too much donor can bedeleterious to cure properties. Preferably, the sensitizer is present inabout 0.05-5 weight percent based on resin compounds of the overallcomposition. More preferably, the sensitizer is present at 0.10-1.0weight percent. Similarly, the iodonium initiator is preferably presentat 0.05-10.0 weight percent, more preferably at 0. 10-5.0 weightpercent, and most preferably 0.50-3.0 weight percent. Likewise, thedonor is preferably present at 0.01-5.0 weight percent, more preferably0.05-1.0 weight percent, and most preferably 0.05-0.50 weight percent.

[0072] The cationically polymerizable epoxide useful in the compositionsof the invention are organic compounds having an oxirane ring, i.e., agroup of the formula:

[0073] which is polymerizable by ring opening. Such materials, broadlycalled epoxides, include monomeric epoxy compounds and epoxides of thepolymeric type and can be aliphatic, cycloaliphatic, aromatic orheterocyclic. These materials generally have, on the average, at least 1polymerizable epoxy group per molecule, preferably at least about 1.5and more preferably at least about 2 polymerizable epoxy groups permolecule. The polymeric epoxides include linear polymers having terminalepoxy groups (e.g., a diglycidyl ether of a polyoxyalkylene glycol),polymers having skeletal oxirane units (e.g., polybutadienepolyepoxide), and polymers having pendent epoxy groups (e.g., a glycidylmethacrylate polymer or copolymer). The epoxides may be pure compoundsor may be mixtures of compounds containing one, two, or more epoxygroups per molecule. The “average” number of epoxy groups per moleculeis determined by dividing the total number of epoxy groups in theepoxy-containing material by the total number of epoxy-containingmolecules present.

[0074] These epoxy-containing materials may vary from low molecularweight monomeric materials to high molecular weight polymers and mayvary greatly in the nature of their backbone and substituent groups. Forexample, the backbone may be of any type, and substituent groups thereoncan be any group that does not substantially interfere with cationiccure at room temperature (RT). Illustrative of permissible substituentgroups include halogens, ester groups, ethers, sulfonate groups,siloxane groups, nitro groups, phosphate groups, and the like. Themolecular weight of the epoxy-containing materials may vary from about58 to about 100,000 or more.

[0075] Useful epoxy-containing materials include those which containcyclohexene oxide groups, such as epoxycyclohexanecarboxylates, typifiedby 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (UVR6105 or 6105),3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, diglycidyl ether of bisphenol A, vinyl cyclohexene dioxide(ERL 4206 or 4206), butanediol diglycidyl ether (RD 2), andbis(3,4-epoxy-6-methylcyclohexylmethyl) adipate. For a more detailedlist of useful epoxides of this nature, reference is made to the U.S.Pat. No. 3,117,099, which is incorporated herein by reference.

[0076] Further epoxy-containing materials which are useful in thecompositions of this invention include glycidyl ether monomers of theformula:

[0077] where R′ is alkyl or aryl and n is an integer of 1 to 6. Examplesof these materials are glycidyl ethers of polyhydric phenols obtained byreacting a polyhydric phenol with an excess of chlorohydrin such asepichlorohydrin (e.g., the diglycidyl ether of2,2-bis-(2,3-epoxypropoxyphenol)-propane). Further examples of epoxidesof this type are described in U.S. Pat. No. 3,018,262, which isincorporated herein by reference, and in “Handbook of Epoxy Resins” byLee and Neville, McGraw-Hill Book Co., New York (1967).

[0078] There are a host of commercially available epoxy resins which canbe used in this invention. In particular, epoxides which are readilyavailable include octadecylene oxide, epichlorohydrin, styrene oxide,vinyl cyclohexene oxide, glycidol, glycidylmethacrylate, diglycidylether of Bisphenol A (e.g., those available under the trade designations“Epon 828”, “Epon 825”, “Epon 1004” and “Epon 1010” from Shell ChemicalCo., “DER-331”, “DER-332”, and “DER-334”, from Dow Chemical Co.),vinylcyclohexene dioxide (e.g., “ERL-4206” from Union Carbide Corp.),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate (e.g.,“ERL-4221” or “CYRACURE UVR 6110” or UVR 6105” from Union CarbideCorp.),3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexenecarboxylate (e.g., “ERL-4201” from Union Carbide Corp.),bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate (e.g., “ERL-4289” fromUnion Carbide Corp.), bis(2,3-epoxycyclopentyl) ether (e.g., “ERL-0400”from Union Carbide Corp.), aliphatic epoxy modified from polypropyleneglycol (e.g., “ERL-4050” and “ERL-4052” from Union Carbide Corp.),dipentene dioxide (e.g., “ERL-4269” from Union Carbide Corp.),epoxidized polybutadiene (e.g., “Oxiron 2001” from FMC Corp.), siliconeresin containing epoxy functionality, halogenated epoxy resins (e.g.,“DER-580”, a brominated bisphenol type epoxy resin available from DowChemical Co., which is flame retardant), 1,4-butanediol diglycidyl etherof phenolformaldehyde novolak (e.g., “DEN-431” and “DEN-438” from DowChemical Co.), and resorcinol diglycidyl ether (e.g., “Kopoxite” fromKoppers Company, Inc.), bis(3,4-epoxycyclohexyl)adipate (e.g.,“ERL-4299” or “UVR-6128”, from Union Carbide Corp.),2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-meta-dioxane(e.g., “ERL-4234” from Union Carbide Corp.), vinylcyclohexene monoxide1,2-epoxyhexadecane (e.g., “UVR-6216” from Union Carbide Corp.), alkylglycidyl ethers such as alkyl C₈-C₁₀ glycidyl ether (e.g., “HELOXYModifier 7” from Shell Chemical Co.), alkyl C₁₂-C₁₄ glycidyl ether(e.g., “HELOXY Modifier 8” from Shell Chemical Co.), butyl glycidylether (e.g., “HELOXY Modifier 61” from Shell Chemical Co.), cresylglycidyl ether (e.g., “HELOXY Modifier 62” from Shell Chemical Co.),p-ter butylphenyl glycidyl ether (e.g., “HELOXY Modifier 65” from ShellChemical Co.), polyfunctional glycidyl ethers such as diglycidyl etherof 1,4-butanediol (e.g., “HELOXY Modifier 67” from Shell Chemical Co.),diglycidyl ether of neopentyl glycol (e.g., “HELOXY Modifier 68” fromShell Chemical Co.), diglycidyl ether of cyclohexanedimethanol (e.g.,“HELOXY Modifier 107” from Shell Chemical Co.), trimethylol ethanetriglycidyl ether (e.g., “HELOXY Modifier 44” from Shell Chemical Co.),trimethylol propane triglycidyl ether (e.g., “HELOXY Modifier 48” fromShell Chemical Co.), polyglycidyl ether of an aliphatic polyol (e.g.,“HELOXY Modifier 84” from Shell Chemical Co.), polyglycol diepoxide(e.g., “HELOXY Modifier 32” from Shell Chemical Co.), bisphenol Fepoxides (e.g., “EPN-1138” or “GY-281” from Ciba-Geigy Corp.),9,9-bis[4-(2,3-epoxypropoxy)-phenyl]fluorenone (e.g., “Epon 1079” fromShell Chemical Co.).

[0079] Other useful epoxy resins are well known and contain suchepoxides as epichlorohydrins, alkylene oxides, e.g., propylene oxide,styrene oxide; alkenyl oxides, e.g., butadiene oxide; glycidyl esters,erg., ethyl glycidate. The polymers of the epoxy resin can optionallycontain other functionalities that do not substantially interfere withcationic cure at room temperature.

[0080] Blends of various epoxy-containing materials are alsocontemplated in this invention. Examples of such blends include two ormore weight average molecular weight distributions of epoxy-containingcompounds, such as low molecular weight (below 200), intermediatemolecular weight (about 200 to 10,000) and higher molecular weight(above about 10,000). Alternatively or additionally, the epoxy resin maycontain a blend of epoxy-containing materials having different chemicalnatures, such as aliphatic and aromatic, or functionalities, such aspolar and non-polar. Other cationically polymerizable polymers canadditionally be incorporated, if desired.

[0081] The terms “polyol” and “hydroxyl-containing material” are usedherein interchangeably. The hydroxyl-containing material which is usedin the present invention can be any organic material having hydroxylfunctionality of at least 1, and preferably at least 2.

[0082] Preferably, the hydroxyl-containing material contains two or moreprimary or secondary aliphatic hydroxyl groups (i.e., the hydroxyl groupis bonded directly to a non-aromatic carbon atom). The hydroxyl groupscan be terminally situated, or they can be pendent from a polymer orcopolymer. The molecular weight of the hydroxyl-containing organicmaterial can vary from very low (e.g., 32) to very high (e.g., onemillion or more). Suitable hydroxyl-containing materials can have lowmolecular weights, i.e. from about 32 to 200, intermediate molecularweight, i.e. from about 200 to 10,000, or high molecular weight, i.e.above about 10,000. As used herein, all molecular weights are weightaverage molecular weights.

[0083] The hydroxyl-containing material can optionally contain otherfunctionalities that do not substantially interfere with cationic cureat room temperature. Thus, the hydroxyl-containing materials can benonaromatic in nature or can contain aromatic functionality. Thehydroxyl-containing material can optionally contain heteroatoms in thebackbone of the molecule, such as nitrogen, oxygen, sulfur, and thelike, provided that the ultimate hydroxyl-containing material does notsubstantially interfere with cationic cure at room temperature. Thehydroxyl-containing material can, for example, be selected fromnaturally occurring or synthetically prepared cellulosic materials. Ofcourse, the hydroxyl-containing material is also substantially free offunctionality which may be thermally or photolytically unstable or whichmay interfere with cationic cure; that is, the material will notdecompose or liberate volatile components at temperatures below about100° C. or in the presence of actinic light which may be encounteredduring the desired curing conditions for the photocopolymerizablecomposition.

[0084] Representative examples of suitable hydroxyl-containing materialshaving a hydroxyl functionality of 1 include alkanols, monoalkyl ethersof polyoxyalkyleneglycols, monoalkyl ethers of alkylene-glycols, andothers known in the art.

[0085] Representative examples of useful monomeric polyhydroxy organicmaterials include alkylene glycols (e.g., 1,2-ethanediol;1,3-propanediol; 1,4-butanediol; 1,6-hexanediol; 1,8-octanediol;2-ethyl-1,6-hexanediol; bis(hydroxymethyl)cyclohexane;1,18-dihydroxyoctadecane; 3-chloro-1,2-propanediol); polyhydroxyalkanes(e.g., glycerine, tri-methylolethane, pentaerythritol, sorbitol) andother polyhydroxy compounds such as N,N-bis(hydroxyethyl)benzamide;2-butyne-1,4-diol; 4,4-bis(hydroxymethyl)diphenylsulfone; castor oil;and the like.

[0086] Representative examples of useful polymerizablehydroxyl-containing materials include polyoxyethylene andpolyoxypropylene glycols, and particularly the polyoxyethylene andpolyoxypropylene glycol diols and triols having molecular weights fromabout 200 to about 10,000 corresponding to a hydroxy equivalent weightof 100 to 5000 for the diols or 70 to 3300 for triols;polytetramethylene ether glycols such as polytetrahydrofuran or “polyTHF” (pTHF) of varying molecular weight; copolymers of hydroxypropyl andhydroxyethyl acrylates and methacrylates with other freeradical-polymerizable monomers such as acrylate esters, vinyl halides,or styrene; copolymers containing pendent hydroxy groups formed byhydrolysis or partial hydrolysis of vinyl acetate copolymers,polyvinylacetal resins containing pendent hydroxyl groups; modifiedcellulose polymers such as hydroxyethylated and hydroxypropylatedcellulose; hydroxy-terminated polyesters; hydroxy-terminatedpolylactones, and particularly the polycaprolactones; fluorinatedpolyoxyethylene or polyoxypropylene glycols; hydroxy-terminatedpolyalkadienes; and 2-oxepanone polymer with2-ethyl-2-(hydroxymethyl)-1,3-propane diol.

[0087] Useful commercially available hydroxyl-containing materialsinclude the “TERATHANE” series of polytetramethylene ether glycols suchas “TERATHANE” 650, 1000, 2000 and 2900 (available from du Pont deNemours, Wilmington, Del.) the “PEP” series of polyoxyalkylene tetrolshaving secondary hydroxyl groups such as “PEP” 450, 550 and 650;“BUTVAR” series of polyvinylacetal resins such as “BUTVAR” B-72A, B-73,B-76, B-90 and B-98 (available from Monsanto Chemical Company, St.Louis, Mo.); and the “FORMVAR” series of resins such as 7/70, 12/85,7/95S, 7/95E, 15/95S and 15/95E (available from Monsanto ChemicalCompany); the “TONE” series of polycaprolactone polyols such as “TONE”0200, 0210, 0230, 0240, 0300 and 0301 (available from Union Carbide);“PARAPLEX U-148” aliphatic polyester diol (available from Rohm and Haas,Philadelphia, Pa.), the “MULTRON” R series of saturated polyesterpolyols such as “MULTRON” R-2, R-12A, R-16, R-18, R-38, R-68 and R-74(available from Mobay Chemical Co.); “KLUCEL E” hydroxypropylatedcellulose having an equivalent weight of approximately 100 (availablefrom Hercules Inc.); “Alcohol Soluble Butyrate” cellulose acetatebutyrate ester having a hydroxyl equivalent weight of approximately 400(available from Eastman Kodak Co., Rochester, N.Y.); polyether polyolssuch as polypropylene glycol diol (e.g., “ARCOL PPG-425”, “ArcolPPG-725”, “ARCOL PPG-1025”, “ARCOL PPG-2025”, ARCOL PPG-3025”, “ARCOLPPG-4025” from ARCO Chemical Co.); polypropylene glycol triol (e.g.,“ARCOL LT-28”, “ARCOL LHT-42”, “ARCOL LHT 112”, “ARCOL LHT 240”, “ARCOLLG-56”, “ARCOL LG-168”, “ARCOL LG-650” from ARCO Chemical Co.); ethyleneoxide capped polyoxypropylene triol or diol (e.g., “ARCOL 11-27”, “ARCOL11-34”, “ARCOL E-351”, “ARCOL E-452”, “ARCOL E-785”, “ARCOL E-786” fromARCO Chemical Co.); ethoxylated bis-phenol A; propylene oxide orethylene oxide-based polyols (e.g., “VORANOL” polyether polyols from theDow Chemical Co.).

[0088] The amount of hydroxyl-containing organic material used in thecompositions of the invention may vary over broad ranges, depending uponfactors such as the compatibility of the hydroxyl-containing materialwith the epoxide, the equivalent weight and functionality of thehydroxyl-containing material, the physical properties desired in thefinal cured composition, the desired speed of photocure, and the like.

[0089] Blends of various hydroxyl-containing materials are particularlycontemplated in this invention. Examples of such blends include two ormore molecular weight distributions of hydroxyl-containing compounds,such as low molecular weight (below 200), intermediate molecular weight(about 200 to 10,000) and higher molecular weight (above about 10,000).Alternatively or additionally, the hydroxyl-containing material cancontain a blend of hydroxyl-containing materials having differentchemical natures, such as aliphatic and aromatic, or functionalities,such as polar and non-polar. As an additional example, one may usemixtures of two or more poly-functional hydroxy materials or one or moremono-functional hydroxy materials with poly-functional hydroxymaterials.

[0090] The spiroorthocarbonate compounds (SOCs) used in making thepolymerizable compositions of the present invention are comprised of oneor more compounds of the formula:

[0091] wherein

[0092] R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl or substitutedaryl, or

[0093] R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6;—CH₂-epoxy-(CH₂)_(n)— CH₂— where n=0, 1, and 2; and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, and R₆ and R₇, provided that

[0094] R₃, R₄, R₇, and R₈ are hydrogen when R₁•R₂ and R₅•R₆ areindependently selected from the group consisting of —CH₂(CH₂)_(n)CH₂—where n=3, 4, 5 and 6 so as to form an alicyclic ring between R₁ and R₂and between R₅ and R₆;

[0095] R₂, R₃, R₄, R₆, R₇, and R₈ are hydrogen when R₁ and R₅ areindependently selected from the group consisting of alkyl, aryl,substituted alkyl, and substituted aryl;

[0096] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₆ are independentlyselected from the group consisting of alkyl, aryl, substituted alkyl,and substituted aryl and R₃ and R₇ are independently selected from thegroup consisting of —(CH₂)_(n)—O—(O═C)—R₉ where n=1 and 2 and R₉=H,alkyl, aryl, substituted alkyl or substituted aryl;

[0097] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are independentlyselected from the group consisting of H, alkyl, aryl, substituted alkyl,and substituted aryl and R₆•R₇=—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1,and 2 so as to form an alicyclic ring between R₆ and R₇;

[0098] R₁, R₄, R₅, and R₈ are hydrogen when R₂•R₃ and R₆•R₇ areindependently selected from the group consisting of—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form an alicyclicring between R₂ and R₃ and between R₆ and R₇;

[0099] R₁, R₄, R₅, and R₈ are hydrogen when R₂ is independently selectedfrom the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆ and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl;

[0100] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are independentlyselected from the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl;

[0101] R₃, R₄, R₅, R₆, R₇, and R₈ are independently selected from thegroup consisting of the group consisting of hydrogen, alkyl, aryl,substituted alkyl, and substituted aryl, when R₁•R₂=—O— so as to form anoxirane ring between R₁ and R₂; and

[0102] R₃, R₄, R₇, and R₈ are independently selected from the groupconsisting of the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl, when R₁•R₂ and R₅•R₆ =—O— so as to form anoxirane ring between R₁ and R₂ and between R₅ and R₆.

[0103] Certain spiroorthocarbonates represented by formula (I) above arenovel compounds. These compounds are compounds of formula (I)

[0104] wherein

[0105] R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl and substitutedaryl, or

[0106] R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6 and—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2, and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, or R₆ and R₇; provided that

[0107] R₁, R₄, R₅, and R₈ are hydrogen when R₂ is independently selectedfrom the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy,(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆ and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl;

[0108] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are independentlyselected from the group consisting of 6-oxabicyclo[3.1.0]hex-2-yl,6-oxabicyclo[3.1.0]hex-3-yl, (6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy,(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl;

[0109] R₃, R₄, R₅, R₆, R₇, and R₈ are independently selected from thegroup consisting of the group consisting of hydrogen, alkyl, aryl,substituted alkyl, and substituted aryl, when R₁•R₂=—O— so as to form anoxirane ring between R₁ and R₂;

[0110] R₃, R₄, R₇, and R₈ are independently selected from the groupconsisting of the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl, when R₁•R₂ and R₅•R₆=—O— so as to form anoxirane ring between R₁ and R₂ and between R₅ and R₆;

[0111] R₁, R₄, R₅, and R₈ are hydrogen when R₂ and R₃ are ethyl andR₆•R₇ are —CH₂-epoxy-(CH₂)_(n)—CH₂— where n=1 and 2 so as to form analicyclic ring between R₆ and R₇; and

[0112] R₁, R₄, R₅, and R₈ are hydrogen when R₂•R₃ and R₆•R₇ are—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=1 and 2 so as to form an alicyclicring between R₂ and R₃ and R₆ and R₇.

[0113] These novel compounds include, but are not limited to,5,5-diethyl-19-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′4″-bicyclo[4.1.0]heptane],7,26-dioxatrispiro[bicyclo[4.1.0]heptane-4,5′-1,3-dioxane-2′2″-1,3-dioxane-5″,4″-bicyclo[4.1.0]heptane],5-5-diethyl-18-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′3″-bicyclo[3.1.0]hexane], and6,24-dioxatrispiro[bicyclo[3.1.0]hexane-3,5′-1,3-dioxane-2′2″-1,3-dioxane-5″3′″-bicyclo[3.1.0]hexane],3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-3-yl)methyl]spiro[5.5]undecane,3,9-bis(7-oxabicyclo[4.1.0]hept-3-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-2-yl)methyl]spiro[5.5]undecane,3,9-bis(7-oxabicyclo[4.1.0]hept-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis(6-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane,3,9-bis(6-oxabicyclo[3.1.0hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,9-bis(7-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis(7-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[3.1.0]hex-2-yl)spiro [5.5]undecane, 2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],5,12-dimethyl-2,4,7,9.11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],4,5,5,11-tetramethyl-8,10-13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],and5,5-dimethyl-8,10-13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane].Each of these novel spiroorthocarbonates has at least one epoxyfunctional group.

[0114] The chemical structures of the above-listed novel compounds areas follows:

3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]spiro[5.5]undecane

[0115]

3,9-bis[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0116]

3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]spiro[5.5]undecane

[0117]

3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0118]

3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methyl]spiro[5.5]undecane

[0119]

3,9-bis[(6-oxabicyclo[3.1.0]hex-3-yl)methyl]3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0120]

3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]spiro[5.5]undecane

[0121]

3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0122]

3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[4.1.0]hept-3-yl)methyl]spiro[5.5]undecane

[0123]

3,9-bis[(7-oxabicyclo[4.1.0]hept-3-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0124]

3,3-diethyl-1,5,7,11-tetraoxa-9-[(7-oxabicyclo[4.1.0]hept-2-yl)methyl]spiro[5.5]undecane

[0125]

3,9-bis[(7-oxabicyclo[4.1.0]hept-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0126]

3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane

[0127]

3,9-bis(6-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0128]

3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane

[0129]

3,9-bis(6-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0130]

3,9-bis(7-oxabicyclo[4.1.0]hept-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0131]

3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-3-yl)spiro[5.5]undecane

[0132]

3,9-bis(7-oxabicyclo[4.1.0]hept-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0133]

3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-2-yl)spiro[5.5]undecane

[0134]

2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′-bicyclo[4.1.0]heptane]

[0135]

8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane]

[0136]

5,12-dimethyl-2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′-bicyclo[4.1.0]heptane]

[0137]

4,5,5,11-tetramethyl-8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane]

[0138]

5,5-dimethyl-8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane]

[0139] The SOCs of formula I expand as they undergo ring-openingreactions and are particularly suited for use in reducing shrinkage ofpolymerizable compositions of the present invention. Preferably, theSOCs of formula I are tetraoxaspiroundecanes (TOSUs), which are SOCshaving 2 six-membered rings that have oxygen atoms bonded to the centercarbon.

[0140] The SOCs can be prepared by transesterification oftetraalkylorthocarbonates such as tetraethylorthocarbonate ortetramethylorthocarbonate and the corresponding diol using an aromatichydrocarbon solvent such as toluene or xylene in the presence of acatalytic amount of an organic acid such asp-toluene sulfonic acid. Thereaction is driven to completion by removal of the alcohol and ispurified by distillation or chromatography and/or recrystallization. Thespiroorthocarbonate compounds can also be prepared by other reactionsinvolving thiophosgenation and organotin intermediates. See generally,R. K. Sadhir & R. M. Luck, Expanding Monomers: Synthesis.Characterization and Applications, CRC Press, Boca Raton, Fla. (1992).

[0141] The following examples, Examples 1-14, are given to illustratemethods of making various spiroorthocarbonates that may be used inmaking the polymerizable compositions of this invention. The examplesare to be construed as illustrative and not in a limiting sense. Unlessotherwise indicated, all parts and percentages are by weight, and allmolecular weights are weight average molecular weight. Examples 11-14illustrate methods of making certain novel spiroorthocarbonates of thepresent invention.

EXAMPLE 1trans/trans-2,3,8,9-DI(TRIMETHYLENE)-1,5,7,11-TETRAOXASPIRO[5.5]-UNDECANE(DTM₃)

[0142] The sequence of synthetic reactions employed in the preparationof this spiroorthocarbonate is set forth in the following synthesisscheme. cis- and trans-2-Hydroxycyclopentanementhanol diacetates

[0143] Cyclopentene was converted via a Prins reaction to an isomericmixture (1:19) of the diacetate derivatives of the cis:trans diols.Cyclopentene (68 g, 1.0 mol), 100 mL of 37% aqueous formaldehyde (40 g,1.3 mol), and glacial acetic acid (200 mL) were mixed and the mixturecooled to 0° C. Concentrated sulfuric acid (15 mL) was then addeddropwise over a period of 1 hour and the mixture was stirred at roomtemperature for 18 hours. The phases were allowed to separate and theaqueous phase was discarded. The yellow-brown organic phase was washedwith 50 mL of 10% aqueous sodium bicarbonate, 50 mL of 20% aqueoussodium bisulfite, 50 mL of distilled water, and 50 mL of aqueous sodiumchloride. The organic phase was taken up in ether, dried over anhydrousmagnesium sulfate, filtered, and the filtrate evaporated to obtain adark liquid. The crude product was distilled at reduced pressure througha 50-cm vacuum jacketed column fitted with a spiral titanium wire toobtain 110 g (55% yield) of a 1:19 mixture of cis- andtrans-2-hydroxycyclopentanementhanol diacetates (bp 91° to 93° C. at 4.8mmHg).

[0144] cis- and trans-2-Hydroxycyclopentanemethanols

[0145] Transesterification of the diacetate mixture using sodiummethoxide in methanol liberated an isomeric diol mixture. The mixture ofisomeric diacetates (103 g, 0.5 mol) was dissolved in 500 mL ofmethanol, and the mixture was made weakly alkaline with 1 to 2 g sodium.The color turned to light yellow, and a strong smell of methyl acetatewas evident. A mixture of methyl acetate and methanol was then distilledoff in the range of 57° to 70° C. at atmospheric pressure using afractionating still. The viscous residue was neutralized with a fewmilliliters of acetic acid. A small forerun with a strong smell offormaldehyde was first removed by distillation at waterpump pressure,and the diol mixture was finally distilled under reduced pressure toobtain (43 g, 96% yield) of product (bp 110° to 118° C. at 3.7 mmHg).

[0146] trans-2-Hydroxycyclopentanemethanol

[0147] The diol mixture was treated with anhydrous cupric sulfate anddry acetone to selectively convert the cis-isomer to an acetonide. Theparticulate matter was removed by filtration and the filtrate distilled,isolating the acetonide in the first fraction (26° to 28° C.; 1 mmHg),and the trans-diol 5 thereafter (96° to 99° C.); 1 mmHg, 121° to 125°C.; 6 mmHg, 137° to 140° C.; 13 mmHg). The acetonide can be convertedback to the cis-diol by hydrolysis.

[0148]trans/trans-2,3,8,9-Di(trimethylene)-1,5,7,11-tetraoxaspiro[5.5]undecane

[0149] trans-Diol 5 (30.6 g, 0.264 mol) and o-xylene (250 mL) were addedto a flame-dried flask fitted with a Dean-Stark trap and refluxcondenser. The reaction mixture was refluxed (140° C.) with azeotropicremoval of water over 1.5 h. Upon cooling to room temperature, themixture became turbid. Driedp-toluenesulfonic acid (PTSA) (0.7 g) andtetraethyl orthocarbonate 6 (26.2 g 97%, 0.132 moles) were added to thereaction mixture, which subsequently begin to clarify. The reaction wasagain heated, and 26.5 mL ethanol was collected within the first hour.The reaction was maintained at 108° C. overnight. An additional 1.8 mLethanol was collected after heating for 2 h at 130° to 137° C. (Totalethanol collected and removed: 28.3 mL, 31 mL theory.) After cooling toroom temperature, the PTSA was neutralized (−pH 7) with triethylamine(0.7 to 0.8 mL). o-Xylene was removed by rotary evaporation at 66° to70° C. using a water aspirator and then at room temperature, using amechanical pump. The residue oil (40.7 g) was stirred 700 mL hexane andwarned to 60° C. to obtain a homogenous solution. After addition ofmagnesol 30/40 (10 g) and anhydrous MgSO₄ (10 g), heating was continuedat 60° C. for 20 min. The mixture was filtered in vacuo two times, oncehot and once at room temperature, using a small amount of methylenechloride to keep the oil in solution. Solvents were removed using arotary evaporator at room temperature using a water aspirator and thenat 60° to 70° C. using a mechanical pump.

[0150] The residual oil (29.2 of 31.1 g) was transferred to a 50-mLpear-shaped flask. The oil was distilled under vacuum using a short pathdistillation apparatus to yield 9.6 g of an oil solid. It was noted thatthe main compound (135° to 153° C.; 0.20 to 0.55 mmHg) readilycrystallized at 145 ° to 149° C; 0.20 to 0.35 mmHg. In order to obtainanalytical sample, 3.33 g of the oil solid was recrystallized from dryacetone (3.33 g) to yield 0.21 g of 7. Crystals were filtered and driedat room temperature in vacuo. DSC 180.1° C.; ¹H NMR (300 MHz, CDCl₃) δ4.0 to 4.2 (m, 4H), 3.6 to 3.9 (m, 2H), 1.5 to 2. (m, 12H), 1.1 to 1.2(m, 2H); ¹³C NMR (75 MHz, CDCl₃) δ 116.46, 78.56, 77.29, 68.57, 67.70,40.94, 40.82, 27.88, 27.83, 21.85, 21.76, 19.22, 187.99; IR(photoacoustic) 2960, 2914, 2875, 1397, 1324, 1243, 1213, 1197, 1116,1073, 1001, 951 cm⁻¹. Anal. calcd. for C₁₃H₂₀O₄; C, 64, 988; H, 8.39.Found C, 64.18; H, 8.68.

EXAMPLE 2trans/trans-2,3,8,9-DI(TETRAMETHYLENE)-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DTM₄)

[0151] This spiroorthocarbonate was synthesized by the sequence ofpreparative reactions summarized in the appended synthetic scheme.4,5-Tetramethylene-1,3-dioxane

[0152] This dioxane was prepared by the Prins reaction of cyclohexeneand formaldehyde via a reported procedure. To a stirred solutionconsisting of 1200 mL aqueous formaldehyde (37%) and 80 mL conc. H₂SO₄in a 2-L three-neck flask was added (all at once) 408 mL (4 moles) ofcyclohexene. The reaction flask was fitted with a thermometer and areflux condenser. The mixture was continuously stirred and heated toreflux (˜70° C.) for 14 to 16 hr. After the mixture had cooled to roomtemperature, it was transferred to a large separatory funnel, and theorganic and aqueous phases allowed to separate. The aqueous layer(bottom) was drained off and set aside. An equal volume of anhydrousdiethyl ether was added to the organic phase. The mixture was washedsuccessively with 200-mL aliquots of the following aqueous solutions: 10wt % NaHCO₃, 20% NaHSO₃, deionized H₂O, and brine (saturated NaCl).After each wash, the aqueous phase was allowed to separate, and wasdrained off and combined with the original aqueous layer which had beenset aside earlier. (Note: Washing procedure: shake vigorously for 3 to 5min; vent separatory funnel frequently to prevent pressure buildup.) Thewashed organic layer was then dried over MgSO₄, filtered through flutedpaper, and concentrated on a rotary evaporator to remove residualsolvents. The crude dioxane was then distilled at reduced pressure(water aspirator, 15 to 35 mm) either through a Vigreux column, or aClaison head fitted with an ice-water-jacketed condenser and graduatedreceiver. The fraction at 89° to 104° C. (head temperature) wascollected (expected yield 60% to 82%, 340 to 454 g; practical yieldsless than 300 g). Note: The original aqueous phase and water washingscan be extracted with ether reclaim any product which may have beenpartitioned into the aqueous phase. The extract is then subject to thesame series of washings, drying, filtering, and concentrating as theoriginal organic layer.

[0153] 3,4-Tetramethylene-2-oxa-1,5-pentanediol diacetate

[0154] The diacetate was prepared by an established acetylation method.To 156.1 g of magnetically stirred 4,5-tetramethylene-1,3-dioxane in a500-mL Erlenmeyer flask was added rapidly an acetylating mixtureconsisting of 156.1 g acetic anhydride and 1 g conc. H₂SO₄. The colorwent from water white to light blue, to dark blue-green, and finally todark brown. After stirring for several hours at room temperature, themixture was allowed to stand overnight. The reaction mixture was thenneutralized with 4 g of sodium acetate (the color became straw yellow)and filtered through fluted filter paper into a 500-mL round bottomstill pot. The excess acetic anhydride was distilled off using a wateraspirator vacuum (head temp. 60° to 76° C., pot temp. 74° to 131° C., 40mm). Distillation was continued using a mechanical pump vacuum through aClaison head or 6-in. Vigreux column. After raking a precut (pot 72° to115° C., head 32° to 75° C., 0.35 to 0.20 mmHg), the diacetate fraction(pot 128° to 155° C., head 1000 to 130° C., 0.45 mmHg) was collected.The yield was 196.6 g.

[0155] trans-2-Hydroxymethyl-1-cyclohexanol

[0156] The diol was prepared from the diacetate by transesterification.The diacetate (196 g) was dissolved in 500 mL methanol in a 1-LErlenmeyer flask. To the magnetically stirred mixture was added slowlyin small pieces 1.2 g metallic sodium. The mixture was a light yellowcolor with the odor of methyl acetate. Stirring was continued until allthe sodium had reacted. The mixture was transferred to a 1-Lround-bottom flask, and the methyl acetate/methanol components stilledoff at atmospheric pressure (pot 62° to 115° C., head 55° to 75° C.).Upon cooling, the reaction mix neutralized with 2 to 3 mL acetic acid.After changing to water aspirator vacuum, the mixture was distilledthrough a four-plate Oldershaw column. A precut with the odor offormaldehyde was removed (pot 32° to 142° C., head 22° to 50° C., ˜40mmHg). After cooling somewhat, the distillation was continued using amechanical pump vacuum and the diol fraction collected (pot 134° to 137°C., head 81° to 110° C., 135 to 0.4 mmHg). The yield was 99 g.

[0157] Dibutyltin trans-2-hydroxymethyl-1-cyclohexanol adduct

[0158] The dibutyltin intermediate-was prepared by a synthetic procedurereported in the literature. The diol 4 (80.4 g, 0.61 moles) wasdissolved in 1 L toluene and transferred to a three-neck, 2-L flaskfitted with a mechanical stirrer, thermometer, Dean Stark trap withextension adapter, and a reflux condenser. To the stirred reactionmixture was added 153.8 g 98% purity di-n-butyltin oxide, (Bu)₂SnO. Themixture was then heated to reflux to azeotrope off the water ofreaction. Initially, considerable foaming resulted and care was taken toprevent overflow into the Stark trap. The last traces of H₂O were slowlyremoved at reflux (4 to 5 hr); total H₂O collected: ˜11 mL. The mixture(a deep orange-brown color) was cooled to room temperature.

[0159]trans/trans-2,3,8,9-Di(tetramethylene)-1,5,7,11-tetraoxaspiro[5.5]undecane

[0160] The reaction flask containing the dibutyltin intermediate wasfitted with an addition funnel and cold finger condenser (dry ice,acetone). Over a period of 2 hr, 38 to 39 mL of CS₂was added dropwise tothe stirred mixture. After addition was completed, the reaction flaskwas refitted with a thermometer and reflux condenser and heated atreflux (105°-110° C.) for about 21 hr. After cooling to roomtemperature, toluene excess CS₂ were stripped off using a rotaryevaporator with water aspirator and then mechanical pump. The strippedresidue was then distilled at reduced pressure. After removal of a smallprecut, the main product fraction was collected (pot 187° to 220° C.;head 1700 to 205° C., 0.125 to 0.1 mmHg). The yield of crude product, aclean colorless oil was 83.65 g. The distilled product wasrecrystallized twice from hexane (1 g/mL) to obtain the final product.DSC 86.6° C.; ¹H NMR (300 MHz, CDCl₃) δ 3.2 to 4.0 (m, 6H), 1.8 to 2.0(m, 10H), 1.45 to 1.6 (m, 1H), 1.2 to 1.45 (m, 6H), 0.8 to 1.0 (m, 1H);¹³C NMR (75 MHz, CDCL₃) δ 115.08, 76.32, 76.26, 75.34, 75.22, 67.52,66.63, 66.52, 39.70, 39.65, 39.58, 31.16, 31.08, 25.55, 25.50, 25.47,24.92, 24.40, 24.36, 24.26, 24.21; IR (photoacoustic) 2952, 2933, 2867,1246, 1217, 1163, 1108, 1033, 927 cm⁻¹. Anal. calcd. for C₁₅H₂₄O₄; C,67.14; H, 9.01. Found: C, 66.71; H, 8.98.

EXAMPLE 3trans/trans-2,3,8,9-DI(TETRAMETHYLENE)-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DTM₄) (Alternate Procedure)

[0161] The subject spiroorthocarbonate has also been prepared fromtrans2-hydroxymethyl-1-cyclohexanol according to the following method,which is summarized in the following synthesis scheme, and based on areported procedure.

[0162] A 1-L round bottom flask was charged with 65.7 g (0.505 mole)diol and 500 mL toluene, and fitted with a Dean-Stark trap, refluxcondenser, and thermometer. The diol/toluene mixture was heated atreflux, with magnetic stirring, under N₂ for 1.5 hr to azeotrope off anywater, and then allowed to cool to RT. Any toluene/water collected inthe Dean-Stark trap was removed. p-Toluenesulfonic acid (PTSA, 0.1 g)and tetraethyl orthocarbonate (TEOC) (42.7 g, 0.222 mole) were added tothe reaction flask, and the mixture was slowly warmed under N₂ todistill off the ethanol by-product. When the distillation temperaturereached 110° C., the distillation apparatus was disconnected, and thereaction mixture was refluxed overnight (˜16-18 hr) under N₂. Aftercooling to room temperature, the mixture was neutralized withtriethylamine (1.5 to 2.0 mL), and the toluene distilled off under wateraspirator pressure. After cooling to RT, the mixture was taken up to 500mL hexanes and dried by stirring for 15 to 30 mm with a 3 g mixture of1:1 anhydrous MgSO₄: Magnesol. The mixture was filtered, and low boilingimpurities were removed at reduced pressure, and the product wasseparated by simple distillation under high vacuum, yielding 48.5 g(81.5%) of an oil (bp=140-143° C. at 0.25 mmHg). The oil wascrystallized from ˜30 mL hexanes to give 28.2 g (47.4%) of the solidspiroorthocarbonate 3, m.p. by DSC=86.6° C. Yields of oil and solid arebased on the theoretical amount of SOC expected from 0.222 moles ofTEOC.

EXAMPLE 4trans/trans-2,3,8,9-DI(HEXAMETHYLENE)-1,5,7,11-TETRAOXASPIRO-[5.5]UNDECANE(DHM)

[0163] The sequence of synthetic reactions employed in the preparationof this spiroorthocarbonate is set forth in the following synthesisscheme.

[0164] 2-Carboethoxycyclooctanone

[0165] The keto-ester was prepared by the sodium hydride inducedacylation of cyclooctanone (1 using diethyl carbonate). A 1-L roundbottom flask was charged with NaH (60% dispersion in mineral oil, 17.0g, 708 mmol). The Nail was washed with three portions of toluene (200mL), diethyl carbonate (36 mL, 207 mmol) was charged to the flask, andthe reaction mixture warmed to 80° C. A solution of cyclooctanone (18.76g, 149 mmol) in toluene (50 mL) was added dropwise over 1 hr. Thetemperature was maintained at 80° C. for 1.5 hr after the addition ofcyclooctanone. Upon cooling to room temperature, glacial acetic acid (30mL) was added dropwise, followed by ice water (200 mL). The reactionmixture was stirred until all the solid was in solution (additionalwater may be necessary). The layers were separated, and the aqueouslayer was extracted with toluene (3×100 mL). The organic layer was driedover MgSO₄, filtered, and evaporated in vacuo to yield an oil.Purification was achieved by simple high vacuum distillation (91°-93° C.0.5 to 0.6 mmHg) to yield 20.8 g, 71% of 6; IR (neat) 2950, 2870, 1745,1710, 1640, 1617, 1468, 1382, 1330, 1250, 1230, 1185, 1100 cm⁻; ¹H NMR(CDCl₃, 300 MHz) δ (keto-enol mix) 1.23 (t), 1.29 (t), 1.33 to 1.58 (m),1.62 to 1.76 (m), 1.85 to 1.95 (m), 2.32 to 2.68 (m), 3.5 to 3.6 (m),4.1 to 4.25 (m), 12.6 (s, enol H).

[0166] 2-Carboethoxycyclooctanol

[0167] The hydroxy-ester was prepared by reduction of the keto-esterwith sodium borohydride. A 100-mL round bottom flask was charged withketo-ester 2 (5.0 g 25.3 mmol) and ethanol (50 ′mL). The reactionmixture was stirred and NaBH₄ (1.0 g, 26.7 mmol) was added slowly. Thereaction was stirred at RT for 1 hr and monitored by TLC (5:1 hexanes:ethyl acetate). The excess NaBH₄ was quenched by carefully adding aceticacid until no bubbles are evolved and pH is ˜7. The reaction mixture waspoured into EtOAc (250 mL) and washed with water (1×50 mL), followed bybrine (1×50 mL). The organic layer was dried over MgSO₄, filtered andevaporated in vacuo. The remaining oil was subjected to high vacuum inorder to remove the last traces of solvent. The crude oil (4.6 g) wastaken on to the next step without further purification. Crude IRindicated reaction was successful. ¹H NMR (CDCl₃, 300 MHz) δ (t, 3H),1.40-2.50 (m, 12H), 2.7 (m, 1H), 2.8 (brs, 1H), 3.8 (m, 1H), 4.2 (q,2H).

[0168] trans-2-Hydroxymethylcyclooctanol

[0169] The diol was prepared by reduction by the hydroxy-ester withlithium aluminum hydride. A 500-mL round bottom flask was charged withhydroxy-ester (4.6 g, 23 mL) and diethyl ether (150 mL) and blanketedwith N₂. The mixture was cooled to −78° C. using a dry ice/isopropanolbath. Lithium aluminum hydride (1.0 g) was added slowly to the cooledsolution. The reaction was allowed to warm to RT and was added slowly tothe cooled solution. The reaction was allowed to warm to RT and stirovernight. The excess LiAlH₄ was quenched by first adding EtOAc (10 mL)followed by a saturated solution of Rochelle's salt (10 mL). CAUTION:the quench should be done slowly to avoid bubbling over. The reactionmixture was poured into a separatory funnel containing ethyl acetate(150 to 200 mL). The layers were separated and the organic layer waswashed with water (1×25 mL), the brine (1×25 mL). The organic layer wasdried over MgSO₄, filtered, and evaporated in vacuo to yield a colorlessoil. High vacuum distillation (99°-101° C. 0.2 mmHg) yielded 72% of thediol. IR (neat) 3320, 2910, 2850, 1468, 1446, 1034 cm⁻¹, ¹H NMR, (CDCl₃,300 MHz) δ 1.25 to 1.95 (m, 13H), 2.9 (s, 2H), 3.7 (m, 2H), 4.1 (m, 1H);¹³C NMR (CDCl₃, 75 Mhz) δ 22.08, 23.74, 25.45, 27.31, 27.42, 32.66,41.65, 67.61, 73.18. Anal. Calcd. for C₉H₁₈O₂: C, 68.31; H, 11.46.Found: C, 68.84; H, 11.91.

[0170]trans/trans-2,3,8,9-di(hexamethylene)-1,5,7,11-tetraoxaspiro[5.5]undecane

[0171] The spiroorthocarbonate was prepared by reaction of thedibutyltin/diol adduct with carbon disulfide. A 250-mL round bottomflask, blanketed with N₂, was charged with C₈-diol 4 (5.1 g, 31.6 mmol),toluene (100 mL), and dibutyltin oxide (7.9 g, 31.7 mmol). The reactionmixture was slowly warmed to reflux using a Dean-Stark trap to collectwater. Azeotropic removal of water was continued overnight. The reactionmixture was cooled to RT then to 0° C. Carbon disulfide (1.9 mL, 31.6mmol) was added to the reaction mixture dropwise using a syringe. Uponcomplete addition of carbon disulfide the reaction mixture was allowedto warm to RT followed by gentle heating to reflux. Reflux was continuedovernight. The reaction mixture was cooled to RT. Toluene was removed invacuo, and the remaining oil was purified by flash column chromatographyusing a 3.0 cm ID column. Hexane (500 mL+) was used to pack the column,load column, and collect some fractions. The hexane was followed by 10:1hexanes; EtOAc (1 L) as eluent. The fractions were evaporated in vacuoto yield 4.8 g of a clear oil which was taken up in 9 mL hexane and leftin a refrigerator to crystallize. The 0.8 g of 6 was isolated, mp 103°to 105° C., and 4.0 g of oil were recovered (R_(f)2:1 hexanes:EtOAc;0.59); IR(neat) 2930, 1471, 1452, 1231, 1214, 1161, 1130, 1058, 995 cm⁻;¹H NMR (CDCL₃, 300 MHz) δ 1.2 to 2.2 (m, 13H), 3.5 to 3.7 (m, 1H), 4.0to 4.15 (m, 1H), 4.2 to 4.4 (m, 1H); ¹³C NMR (CDCl₃, 75 MHz) δ 22.59,23.15, 24.93, 25.00, 25.81, 26.03, 26.47, 26.68, 28.25, 28.46, 29.13,29.29, 36.24, 36.55, 68.88, 69.24, 73.99, 74.76, 119.59. Anal. Calcd.for C₁₉H₃₂O₄: C, 70.33; H, 9.94. Found: C, 70.06, H, 10.14.

[0172] Inspection of the DSC of the C₈-SOC 6, indicates that there arepossibly two melting points. A study was conducted to determine if thedifference was simply a difference in the conformation of the 8-memberedring. The C₈-SOC was heated on the DSC to ˜150° C., which is about 25°C. above the first melting point. The compound was cooled and thenheated against to 250° C. Note that the first melting point did notappear in the second run, supporting the speculation that the first peakwas a different conformer. Upon cooling again, the compound was heatedto 400° C. Note there is only one melting point. This study does notconfirm different conformers, but it does support the theory.

EXAMPLE 5 2,8-DIMETHYL-1,5,7,11-TETPAOXASPIRO[5.5]UNDECANE (DM)

[0173] The synthetic sequence employed in the preparation of thedimethyl spiroorthocarbonate is set forth in the following synthesisschemes.

[0174] To a 500 mL three-necked round-bottomed flask, equipped with areflux condenser, a Dean-Stark trap, a magnetic stir bar and athermometer, was placed 1,3-butanediol 1 (20 mL, 99%, 0.2208 mole) and350 mL of toluene under an atmosphere of nitrogen. The mixture wasbrought to reflux and maintained for 2 hours to azeotropically removeany moisture. The mixture was cooled to room temperature and then acatalytic amount of p-toluenesulfonic acid (PTSA, 0.35 g) was added. Theresulting mixture was allowed to stir at room temperature until thesolution turned clear. To this solution was then addedtetraethylorthocarbonate (TEOC, 99.5%, 21.3 g, 0.1104 mol) and thereaction mixture was brought to reflux. The azeotropic mixture collectedin the Dean-Stark trap was poured into salt water to determine thevolume of EtOH that was generated. A total of 24.5 mL (theoretically,25.9 mL) of EtOH was collected. TLC analysis (silica gel, 60%EtOAc/hexanes) revealed that the starting diol was completely consumedand that a new major spot (R_(f) 0.59) indicated the formation ofproduct. The reaction mixture was then quenched with 2.5 mL oftriethylamine so that the solution was of pH 8-9. The mixture wasconcentrated using a rotary evaporator and dried under vacuum to give21.2 g of oil was concentrated using a rotary evaporator and dried undervacuum to give 21.2 g of oil (pH˜7). The crude material was purified bydistillation through a Vigreaux distilling head (1:1 ratio) and thedesired 2,8-dimethyl-1,5,7,11-tetraoxaspirol[5.5]undecane 2 (DM) wascollected as colorless oil (74-75° C./0.3 mm-Hg) in 84.2% yield (a totalof 17.6 g of oil, of which 1.0 g of white solid was separated). GC (150°C., 5 min, 20° C./min to 225° C.) analysis showed that these materialswere mixture of three diastereomers (oil: 98.2% pure, 20.6% diastereomer1, 60.3% diastereomer 2 and 17.3% diastereomer 3; solid 97.8% pure,50.7% diastereomer 1, 20.9% diastereomer 2 and 26.2% diastereomer 3).¹H-NMR (CDCl₃, 300 MHz) δ 1.18-1.21 (q, 6H), 1.42.-1.49, 1.60-1.70 (2d,4H), 3.895-3.92 (m, 4H), 4.16-4.28 (m, 2H); ¹³C-NMR (CDCl₃, 75 MHz) δ21.02, 21.22, 31.23, 61.24, 61.36, 62.18, 62.30, 67.57, 67.66, 68.50,68.69, 114.55; IR (neat) (cm⁻¹) 2960, 2920, 2880, 1230, 1150, 1135,1090, 1080, 1010, 870.

EXAMPLE 6 2,8-DITRIFLUOROMETHYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DTFM)

[0175] The synthetic sequence employed in the preparation of thisspiroorthocarbonate is set forth in the following synthesis schemes.

[0176] Ethyl 3-Hydroxy-4,4,4-trifluorobutyrate

[0177] To a 1000 mL three-necked round-bottom flask, equipped with areflux condenser, a thermometer and a magnetic stir bar, was placed 36.8g (99%, 0.2 mol) of 1,1,1-trifluoroacetoacetate and 400 mL of ethylether anhydrous (dried over 3 molecular sieves) under an atmosphere ofN₂. The mixture was cooled to 0° C. and the 8.1 g of sodium borohydride(98%, 0.21 mol) was added in several portions over an hour such that thepot temperature was maintained at 2-3° C. The resulting mixture wasallowed to slowly come to 5° C. and stirred for an additional hour. Thecold bath was removed and the reaction mixture was allowed to stir atroom temperature overnight. The reaction mixture was cooled to 10° C.and then neutralized by slow addition of 200 mL of 10% aqueous HClsolution. The resulting mixture was filtered and the organic phaseseparated. The aqueous phase was extracted with ethyl ether (3×75 mL).The organic phases were combined, swirled over anhydrous potassiumcarbonate (K₂CO₃), dried over anhydrous magnesium sulfate (MgSO₄) andconcentrated under reduced pressure to yield 33.4 g (90%) of oil. Thecrude material was carried on to the subsequent reaction without furtherpurification. IR (neat) (cm⁻¹) 3460, 2995, 2950, 1730, 1370, 1280, 1170,1130, 1045, 1020, 950, 880.

[0178] 2,4-Dihydroxy-1,1,1-trifluorobutane

[0179] To a 500 mL three-necked round-bottom flask, equipped with anadditional funnel, a thermometer and a mechanical stirrer, was placed 12g (95%, 0.3 mol) of lithium aluminum hydride suspended in 100 mL ofethyl ether anhydrous. The mixture was cooled to 0° C. and a solution of33.4 g of ethyl 3-hydroxy-4,4,4-trifluorobutyrate in 100 mL of ethylether was then added dropwise over a period of 4 hours such that thereaction temperature was maintained at 0-5° C. The additional funnel wasreplaced with a reflux condenser and the resulting mixture was allowedto come to room temperature while stirring overnight. The reactionmixture was cooled to 0-5° C. and then neutralized to slow addition of200 mL of 10% aqueous HCl solution. The resulting mixture was filteredand the organic phase separated. The aqueous phase was extracted withethyl ether (3.75 mL). The organic phases were combined, dried overanhydrous magnesium sulfate and concentrated under reduced pressure toyield 18.5 g of oil. The crude material was purified by distillation viaan Vigreux column to give 16.5 g (57.3%) product as a mixture of liquidand solid. Further purification by recrystallization from hexanes gave6.6 g of crystals along with 5.1 g of liquid. Mp (DSC) 205.6° C.; ¹H-NMR(CDCl₃, 300 MHz) δ 5.20 (s, 1H), 4.22-4.16 (m, 1H), 3.94-3.87 (m, 2H),2.55 (s, 1H), 2.10-1.84 (m, 2H); ¹³C-NMR (CDCl₃, 300 MHz) δ131.00-119.00 (q, J=1118.1 Hz), 69.80-68.40 (q, J=125.4 Hz), 59.55,31.09; IR (KBr pellet ) (cm⁻¹) 3380, 2980, 2900, 1435, 1390, 1320, 1280,1170, 1135, 1050, Anal. Calcd for C₄H₇F₃O₂: C, 33.30; H, 4.91; F, 39.60,Found: C, 33.25; H, 4.92; F, 37.27.

[0180] 2.8-Ditrifluoromethyl-1,5,7,11-tetraoxaspiro[5.5]undecane (DTFM3)

[0181] To a 500 mL three-necked round-bottom flask, equipped with aDean-Stark trap ( )20 mL), a reflux condenser, a thermometer and amagnetic stir bar, was placed 16 g (0.111 mol) of2,4-dihydroxy-1,1,1-trifluorobutane (2) and 400 mL of toluene under anatmosphere of N₂. The mixture was brought to reflux and maintained atreflux temperature for 2 hours to azeotropically remove any moisture.About 100 mL (5×20 mL) of azeotropic mixture was collected in theDean-Stark trap. The mixture was then allowed to slowly cool to roomtemperature and a catalytic amount (0.3 g) of anhydrouspara-toluenesulfonic acid (PTSA) was added, followed by dropwiseaddition of 11.7 mL (0.056 mol) of tetraethylorthocarbonate (TEOC). Theresulting mixture was brought to reflux to azeotropically remove ethanolgenerated during the reaction. The azeotropic mixture was shaken withsalt water to determine the amount (volume) of ethanol collected. Thereaction was monitored by GC (5 min at 105° C., 120° C./min rise to 225°C., 5 min at 225° C.) and/or TLC (silica gel, 15% ether/hexanes). Aftera total of 160 mL of azeotropic mixture (12.6 mL of ethanol) wascollected, the reaction mixture was refluxed for an additional 2 hoursand then allowed to stir at 102° C. overnight. The reaction mixture wasallowed to slowly cool to room temperature and then neutralized by theaddition of 1 mL of triethylamine. The resulting mixture was allowed tostir at room temperature for an additional half hour, dried overanhydrous magnesium sulfate, filtered and concentrated chromatography(silica gel, 10-15% ethyl ether/hexanes) to give clear crystals as asingle diastereomer (21% yield) along with two portions (14% and 40%yields, respectively) of liquid as mixture of diastereomers (displayedthe same pattern of mass fragmentation as the crystalline isomer byGC-MS analysis) containing by-products of which the structures were notidentified. Mp (DSC) 122.4° C.; ¹H-NMR (crystalline single diastereomer,CDCl₃, 300 MHz) δ 4.40-4.10 (m, 6H), 2.18-1.71 (m, 4H); ¹³C-NMR(crystalline single diastereomer, CDCl₃, 300 MHz) δ 128.74-117.56 (q,J=1108.5 Hz), 114.52, 70.80-69.44 (q, J=136.2 Hz), 61.21, 22.16; IR(crystalline single diastereomer, KBr pellet) (cm⁻¹) 3010, 2990, 2930,1480, 1440, 1410, 1395, 1330, 1280, 1270, 1240, 1185, 1145, 1110, 1085,1050, 1010, Anal. Calcd for C₉H₁₀F₆O₄: C, 36.50; H, 3.40; F, 38.49;Found: C, 36.50, H, 3.45; F, 36.09.

EXAMPLE 7 2,8-DIPHENYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE AND2,10-DIPHENYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE (DP)

[0182] These spiroorthocarbonates were synthesized by the sequence ofpreparative reactions shown in the following synthesis scheme.

[0183] 3-Phenyl-2-oxa-1,5-pentanediol diacetate

[0184] The diacetate was prepared by an established acetylation method.To 200 g (1.22 moles) of magnetically stirred 4-phenyl-1,3-dioxane in a1-L round bottom (or Erlenmeyer flask) was added rapidly an acetylatingmixture consisting of 200 g (1.95) moles) acetic anhydride and 1 g conc.H₂SO₄. A rapid exotherm to 65° to 70° C. persisting for ≈½ hr wasobserved with a yellow to brown discoloration. After stirring forseveral hours at room temperature, the reactants were allowed to standovernight. The reaction mixture was neutralized with 4 g of sodiumacetate, transferred to a 500-mL round bottom flask, and the excessacetic anhydride was distilled off using a water aspirator vacuum. Thebrown oily residue was then distilled using a mechanical pump vacuum andthe clear, colorless diacetate 2 fraction boiling at 162° to 163W° C./3mm was collected in a yield of 311 g (95% of theory). IR: 1735, 1365,1230, 1120, 1035, 1010, 945, 755, 695 cm⁻¹.

[0185] 1-Phenyl-1,3-propanediol

[0186] The diol was prepared from the diacetate by transesterification.The diacetate (311 g) was dissolved in 600 mL methanol. To thismagnetically stirred mixture was added slowly in small pieces 1.4 g ofmetallic sodium. Stirring was continued until all the sodium had beenadded. The mixture was a light yellow color with the odor of methylacetate. This mixture was transferred to a 1-L round bottom flask andthe methyl acetate/methanol components distilled off at a headtemperature of 57° to 70° C. at atmospheric pressure. Upon cooling, thepot residue was neutralized with 10 mL acetic acid. Neutralized productwas taken up in 3 volumes of anhydrous ether, treated with anhydrousMgSO₄ and Magnesol, filtered, and stripped on the rotovap at up to 75°C., and returned to a still pot. A precut with an odor of formaldehyderemoved up to 100° C. with water aspirator vacuum. The residue wasdistilled under mechanical pump vacuum and the fraction boiling at 140°to 160° C./0.1 mm was collected. The yield of diol was 165.9 g (90% oftheory). The product was a viscous yellow oil which was essentially onecomponent via GC analysis.

[0187] 1-Phenyl-1,3-propanediol dibutyltin adduct

[0188] The dibutyltin intermediate was prepared by a synthetic procedurereported in the literature. Diol 3 (165.9 g, 1.09 moles) was dissolvedin 1L toluene and transferred to a 3-neck, 2-L flask fitted with amechanical stirrer, reflux condenser, thermometer, and a Dean Starktrap. To the stirred reaction mixture was added 277 g 98% purity (1.09moles) of dibutyltin oxide. The mixture was then heated to reflux toazeotrope off the water of reaction. Initially considerable foamingresulted and care was taken to prevent overflow into the Dean Starktrap. The last traces of water were slowly removed at reflux to completethe formation of the dibutyltin adduct. A total of 19 ML was collectedout of 19.6 mL theory.

[0189] 2,8-Diphenyl-1,5,7,11-tetraoxaspiro[5.5]undecane and2,10-Diphenyl-1,5,7,11-tetraoxaspiro[5.5]undecane

[0190] The reaction flask containing was cooled to room temperature andfitted with a dropping funnel and a cold finger condenser (dry ice,acetone). Carbon disulfide (75 mL) was added dropwise to the stirredreaction mixture and slowly heated to reflux (˜95° C.) approximately 1hr. The coldfinger was replaced with a water condenser fitted with adrying tube, and refluxing was continued for an additional 3 hr. Thefinal reflux temp was 100° C. The mixture was allowed to cool to roomtemperature, and the solvent and residual CS₂ stripped off on the rotaryevaporator. The last residual toluene was removed with a mechanical pumpattached to the rotary evaporator.

[0191] The viscous oily residue was extracted with boiling heptane. Oncooling hard crystallites of the SOC were obtained; however, a viscousoil phase also separated. The extraction was repeated several times toobtain more SOC; however, an oil phase was always present. The firstcrystal crop was the purest and after one recrystallization fromheptane, 25 g was obtained as a white hard crystalline mass (m.p. 109°to 111° C.). This product was analyzed by GC at 225° C. and found to be97+% one component, which proved to be the 2,8-diphenyl isomer. Toobtain an analytical sample of each isomer, 9 g of the crystallinematerial was stirred in heptane (90 mL) and heated for 30 min. Limitedsolubility was noted. After cooling to room temperature, the remainingsolid was removed and the mother liquor placed in a crystallizing dish.The mother liquor was allowed to evaporate overnight at roomtemperature. A white crystalline material (0.4 g) and an oily residue(0.6 g) were isolated. The crystals were recrystallized from heptane toyield a rosette-shaped crystalline white solid. The solid isolated inthe first recrystallization was subjected to several recrystallizationsfrom heptane to yield a crystalline white solid.

[0192] 2,8-Diphenyl-1,5,7,11-tetraoxaspiro[5.5]undecane: DSC 128.8° C.;¹H NMR (300 MHz, CDCl₃) δ 7.3 to 7.5 (m, 10H), 5.0 (dd, 2H), 4.5 to 4.6(m, 2H), 4.10 to 4.20 (m, 2H), 2.10 to 2.2 (m, 2H), 1.7 to 1.8 (m, 2H);¹³C NMR (75 MHz, CDCl₃) δ 140.84, 128.48, 127.93, 126.10, 115.51, 73.56,62.73, 32.08; IR (photoacoustic) 3090, 3039, 2962, 2927, 1495, 1457,1389, 1307, 1254, 1213, 1147, 1089, 1009, 861 cm⁻¹. Anal. calcd. forC₁₉H₂₀O₄: C, 73.06; H, 6.45. Found: C, 72.74; H, 6.37.

[0193] 2,10-Diphenyl-1,5,7,11-tetraoxaspiro[5.5]undecane (5b): DSC 99.5°C.; ¹H NMR (300 MHz, CDCl₃) δ 7.26 to 7.46 (m, 10H), 5.36 to 5.43 (dd,1H), 5.01 to 5.38 (dd, 1H), 4.44 to 4.54 (m, 1.H), 4.01 to 4.20 (m, 3H),1.97 to 2.17 (m, 2H), 1.68 to 1.80 (m, 2H), ^(—)C NMR (75 MHz, CDCl₃) δ140.75, 140.56, 128.48, 128.29, 127.99, 127.74, 126.00, 125.80, 115.46,74.28, 73.66, 61.68, 61.83, 32.18, 33.02; IR (photoacoustic) 3066, 3033,3017, 2984, 2927, 1499, 1452, 1386, 1250, 1201, 1150, 1078, 1012, 962cm⁻¹. Anal. calcd. for C₁₉H₂₀O₄; C, 73.06; H, 6.45. Found: C, 73.19; H,6.33.

EXAMPLE 83,9-DIACETOXYMETHYL-3,9-DIETHYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DAMDE)

[0194] The sequence of synthetic reaction employed in the preparation ofthis spiroorthocarbonate is set forth in the following synthesisschemes.

[0195] The title TOSU was prepared via derivatization of thecorresponding parent molecule,3,9-diethyl-3,9-dihydroxymethyl-1,5,711-tetraoxaspiro[5.5]undecane(DEDHM 1), by treatment with acetic anhydride in the presence ofpyridine. To a 250 mL round-bottomed flask was placed3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5.5]undecane(DEDHM 1,5.0 g, 0.018 mol) and pyridine (25 mL) under an atmosphere ofN₂. To this solution was added acetic anhydride (25.5 mL, 0.27 mol). Theresulting mixture was allowed to stir at room temperature for 4 hoursand the reaction progress monitored by TLC. The reaction mixture wasthen concentrated under reduced pressure using a rotary evaporator togive a viscous oil which crystallized upon standing in the refrigeratorovernight. these crystals were further purified by recrystallizationfrom cyclohexane (6.2 g of the crude product was dissolved in 30 mL ofrefluxing cyclohexane, and then allowed to slowly cool to roomtemperature). The crystals were collected by filtration, washed withcyclohexane (3×10 mL) and dried in vacuo. The desired3,9-diacetoxymethyl-3,9-diethyl-1,5,7,11-tetraoxaspiro[5.5]undecane(DAMDE 2) was obtained as white crystals in 81% (5.3 g) yield. Mp (DSC)71.4° C.; ¹H-NMR (CDCl₃, 300 MHz) δ 0.79 (t, 6H), 1.33 (q, 4H), 2.02 (s,6H), 3.71 (m, 4H), 3.79 (m, 4H), 4.14 (s, 4H); ¹³C-NMR (CDCl₃, 75 MHz) δ7.04, 20.70, 23.29, 35.27, 63.34, 66.66, 67.05. 114.60, 170.68; FTIR-PAS(cm⁻¹) 2975, 2940, 2920, 2884, 1463, 1381, 1364, 1259, 1211, 1187, 1104,1076, 1050, 1024, 1000, 969; Anal. Calcd. for C¹ ₁₇H₂₈O₈: C, 56.65; H,7.83; Found: C, 56.89; H, 7.94.

EXAMPLE 93,9-DIETHYL-3,9-DIPROPIONYLOXYMETHYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DEDPM)

[0196] The sequence of synthetic reaction employed in the preparation ofthis spiroorthocarbonate is set forth in the following synthesisschemes.

[0197] The title TOSU was prepared via derivatization of thecorresponding parent molecule,3,9-diethyl-3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5.5]undecane(DEDHM 1), by treatment with propionic anhydride in the presence ofpyridine. To a 100 mL round-bottomed flask was placed3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5.5]undecane(DEDHM 1, 5.0 g, 0.018 mol) and pyridine (25 mL) under an atmosphere ofN₂. To this solution was added propionic anhydride (34.8 mL, 0.27 mol).The resulting mixture was allowed to stir at room temperature for 4hours and the reaction monitored by TLC. Pyridine and any unreactedpropionic anhydride were removed by distillation under reduced pressure(note: the pot temperature should not exceed 40° C. during thedistillation). The vicious residue was then dried in vacuo for 3 hours,which crystallized upon standing at room temperature. The resultingcrystals were purified by recrystallization from cyclohexane (thecrystals were dissolved in 18 mL of cyclohexane, allowed to slowly coolto room temperature and then kept in refrigerator overnight). The whitecrystals were collected by filtration, washed with cyclohexane (3×5 mL)and dried in vacuo. The desired3,9-diethyl-3,9-dipropionyloxymethyl-1,5,7,11-tetraoxaspiro[5.5]undecane(DAMDE 2) was obtained as white crystals in 71.1% (5.0 g) yield. Mp(DSC) 68.1° C.; ¹H-NMR (CDCl₃, 300 MHz) δ 0.81 (t, 6H), 1.11 (t, 6H),1.35 (q, 4H), 2.32 (q, 4H), 3.73-3.81 (m, 8H), 4.15 (s, 4H); ^(—)C-NMR(CDCl₃, 75 MHz) δ 7.10, 9.05, 23.38, 27.44, 35.42, 63.20, 66.74, 67.10,114.66, 174.06; FTIR-PAS (cm⁻¹) 3543, 3524, 2957, 2940, 2913, 2883,2859, 1738, 1460, 1382, 1363, 1262, 1223, 1215, 1190, 1157, 1121, 1083,1070, 1009, 991, 957, 936; Anal. Calcd. for C₁₉H₃₂O₈: C, 58.75; H, 8.30;Found: C, 58.86; H, 8.53.

EXAMPLE 103,9-DIACETOXYMETHYL-3,9-DIPHENYL-1,5,7,11-TETRAOXASPIRO[5.5]UNDECANE(DAMDP)

[0198] The sequence of synthetic reaction employed in the preparation ofthis spiroorthocarbonate is set forth in the following synthesisschemes.

[0199] To a 100 mL round-bottomed flask was placed3,9-dihydroxymethyl-3,9-diphenyl-1,5,7,11-tetraoxaspiro[5.5]undecane(CHMDP 1, 3.8 g, 0.01 mol) and pyridine (23 mL) under an atmosphere ofN₂ (the starting DHMDP was not completely dissolved in pyridine). To themixture was added acetic anhydride (14 mL, 0.15 mL) and the mixturebecame clear solution upon stirring. The reaction mixture was allowed tostir at room temperature for 3 hours and the reaction progress wasmonitored by TLC (2:3 Hexanes/EtOAc). The reaction mixture was thenconcentrated under reduced pressure using a rotary evaporator to give aviscous oil. The crude material was purified by column chromatography(silica gel, 30-50% hexanes/EtOAc; Note: the crude material was absorbedonto small amount of Silica get (˜10 g) and then loaded onto a column(3.0 cm i.d.) packed with ˜100 g of silica gel) to give 4.0 g of whiteviscous oil which was further purified by recrystallization fromcyclohexane (the material was dissolved in 30 mL of refluxingcyclohexane and a sticky solid precipitated upon cooling to roomtemperature). The white solid was then collected by filtration, dried invacuo to give the desired DAMDP 2 in 82.6% (3.8 g) yield. Mp (DSC) 31.0°C. (broad peak); ¹H-NMR (CDCl₃, 300 MHz) δ 1.95 (s, 6H), 4.21 (s, 4H),4.29 (d, 2H), 4.46 (d, 2H), 4.59 (s, 4H), 7.20-7.39 (m, 10H); ¹³C-NMR(CDCl₃, 75 MHz) δ 20.69, 39.17, 65.30, 66.63, 67.09, 114.25, 125.73,128.68, 127.48, 138.41, 170.51; FTIR-PAS (cm⁻¹) 2937, 1749, 1480, 1460,1377, 1255, 1230, 1172, 1120, 1024, 964, 774, 709; Anal. Calcd. forC₂₅H₂₈O₈: C, 65.78; H, 6.18; Found: C, 58.85; H, 6.22.

EXAMPLE11 5,5-DIETHYL-19-OXADISPIRO[1,3-DIOXANE-2,2′-1,3-DIOXANE-5′,4″-BICYCLO[4.1.0]HEPTANE](DECHE)

[0200] (3,3-Diethyl-11,12-epoxy-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadecane)

[0201] The synthetic sequence employed in the preparation of this epoxyspiroorthocarbonate is set forth in the following synthesis schemes.

[0202] 5,5-Diethyl-1,3-dioxane-2-thione (1)

[0203] The thiocarbonate 1 was prepared by a variation of thethiocarbonylation procedure developed by Corey and Hopkins. To athree-necked round-bottomed flask, equipped with a mechanical stirrerand an additional funnel, was placed 2,2-diethyl-1,3-propanediol (15.86g, 120 mmol), 4-dimethylaminopyridine (DMAP, 29.32 g, 240 mmol) and 120mL of toluene under an atmosphere of nitrogen. The mixture was allowedto stir at room temperature until a homogeneous solution was reached.The mixture was cooled to 0-5° C. and then a solution of thiophosgene(9.43 mL, 120 mmol) in 90 mL of toluene was added dropwise via theadditional funnel over a period of 90 min. This resulted in theformation of a bright orange DMAP-thiophosgene complex. After thecompletion of addition, the reaction mixture was allowed to stir for anhour at 0-5° C. and then slowly warmed to room temperature. The reactionmixture was allowed to stir at room temperature for an additional hourand then the precipitated DMAP-HCl salt was removed by filtration. Thefiltrate was concentrated under reduced pressure using a rotaryevaporator. The crude material was purified by recrystallization (thecrude material was dissolved in refluxing ether, allowed to cool to roomtemperature and slowly evaporated) or by column chromatography (silicagel, 2:1 methylene chloride/hexanes). The desired thiocarbonate 1 wasobtained as white crystalline in 70% yield. Mp (DSC) 64.4° C. ¹H-NMR(CDCl₃, 300 MHz) δ 4.17 (s, 4H), 1.51-1.43 (q, 4H, J=7.5 Hz), 0.92-0.87(t, 6H, J=7.5 Hz); ¹³C-NMR (CDCl₃, 75 MHz) δ 189.53, 76.08, 33.67,23.09, 6.97; IR (KBr pellet) (cm⁻¹) 2960, 2920, 1455, 1395, 1380, 1290,1240, 1200, 1180, 1060, 990, 930, 720.

[0204] 3,3-Dibutyl-2,4-dioxa-3-stannaspiro[5.5]undec-8-ene (2)

[0205] The tin adduct 2 and DECH 3 were prepared employing theprocedures developed by Stansbury and Bailey. To a three-neckedround-bottomed flask, equipped with a thermometer, a reflux condenserand a Dean-Start trap with an extension condenser, was placed aheterogeneous mixture of 2,2-cyclohexene-dimethanol (8.48 g, 59.6 mmol,purified by recrystallization from ethyl ether) and dibutyltin oxide(98%, 15.14 g, 59.6 mmol) in 250 mL of toluene. The mixture was broughtto reflux and became clear solution. The reaction mixture was allowed toreflux for 3 hours while the liberated water was collected (withtoluene) in the Dean-Stark trap (5×20 mL of the azeotropic mixture wascollected). The Dean-Stark trap was removed and the reaction mixture wasthen allowed to reflux for additional 2 hours and then slowly cooled toroom temperature under an atmosphere of nitrogen. The3,3-dibutyl-2,4-dioxa-3-stannaspiro[5.5]undec-8-ene 2 thus generated insitu was carried on to the subsequent reaction without furtherpurification.

[0206] Note: The starting diol, 2,2-cyclohexene-dimethanol (98%, ACROS),needed to be purified prior to use, otherwise the reaction would fail toyield the desired tin adduct 2.

[0207] 3,3-Diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene (DECH3)

[0208] To the above solution of3,3-dibutyl-2,4-dioxa-3-stannaspiro[5.5]undec-8-ene 2 was added5,5-diethyl-1,3-dioxane-2-thione 1 (10.39 g, 59.6 mmol) in several smallportions at room temperature over a period of 20 min. The resultingmixture was allowed to stir at room temperature for 24 hours. Thereaction was monitored by TLC (silica gel, 25% ether/hexanes). Thereaction mixture was then concentrated under reduced pressure and theresidue taken up with ethyl ether (white suspension formed uponstanding). The ether solution was filtered and concentrated underreduced pressure to give light yellowish oil. The crude material waspurified by column chromatography (silica gel, 10-15% ethylether/hexanes). The desired3,3-diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene (DECH 3) wasobtained as colorless oil in 94% yield. ¹H-NMR (CDCl₃, 300 MHz) δ5.68-5.58 (m, 2H), 3.74-3.68 (4s, 8H), 2.08-1.94 (m, 4H), 1.63-1.56 (t,2B, J=6.6 Hz), 1.46-1.37 (q, 4H, J=7.5 Hz), 0.84-0.76 (t, 6H, J=7.5 Hz);^(—)C-NMR (CDC₃, 75 MHz) δ 126.03, 124.16, 114.68, 70.03, 69.32, 34.27,30.50, 26.44, 23.14, 21.30, 13.92, 7.01; IR (neat) (cm⁻¹) 3020, 2960,2880, 1640, 1450, 1360, 1250, 1220, 1200, 1185, 1160, 1105, 1020, 995,920, 730, 655; Anal. Calcd for C₁₆H₂₆O₄: C, 68.06%; H, 9.28%; Found: C,68.20%; H, 9.59%.

[0209]5,5-Diethyl-19-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′,4″-[bicyclo[4.1.0]heptane](DECHE 4)

[0210](3,3-Diethyl-11,12-epoxy-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadecane)

[0211] The spiroorthocarbonate 4 was prepared employing the biphasicepoxidation procedure described by Anderson and Veysoglu due to the acidsensitive nature of this class of compounds. To a round-bottomed flaskwas placed 3,3-diethyl-1,5,7,16-tetraoxadispiro[5.2.5.2]hexadec-11-ene(DECH 3, 10.02 g, 35.4 mmol) and 350 mL of methylene chloride (CH₂Cl₂).To this solution was added 0.5 M aqueous solution of sodium bicarbonate(110 mL, pH ˜8). The resulting biphasic mixture was allowed to stirvigorously at room temperature and then m-chloroperbenzoic acid (57-86%mCPBA, 9.00 g, ˜35.77 mmol) was slowly added in several portions over aperiod of 30 minutes. The resulting mixture was allowed to stir for 5hours at room temperature and the reaction progress was monitored by TLC(silica gel, 25% ether/hexanes). The two phases were separated and theorganic phase was washed successively with 1 N aqueous NaOH (2×100 mL)and water 2×100 mL). The organic phases were combined, dried overanhydrous Na₂SO₄, and concentrated under reduced pressure to give anoff-white solid. The crude material was washed with 5 mL of cold ether(pre-cooled at 0° C.) and purified by flash chromatography (silica gel,15% ethyl ether/hexanes) or by recrystallization two times from diethylether/hexanes (the crude material was dissolved in refluxing ether,allowed to cool to room temperature and then hexanes was slowly added).The desired product DECHE 4 was obtained as white crystals in 90% yield.Mp (DSC) 67.4° C.; ¹H-NMR (CDCl₃, 300 MHz, mixture of diastereomers) δ3.70-3.50 (m, 8H), 3.16-3.04 (m, 2H), 2.08-1.92 (m, 2H), 1.80-1.60 (m,2H), 1.44-1.18 (m, 6H), 0.86-0.70 (m, 6H); ^(—)C-NMR (CDCl₃, 300 MHz,mixture of diastereomers) δ 114.53, 71.56, 69.45, 69.33, 68.98, 51.57,50.07, 34.30, 31.43, 29.41, 29.29, 23.21, 23.09, 22.79, 19.86, 13.95,7.07, 7.00; IR (KBr pellet) (cm⁻¹) 2970, 1455, 1365, 1255, 1225, 1205,1180, 1110, 1060, 1020, 1000, 920, 810, 795, 780, 730; Anal. Calcd forC₁₆H₂₆O₅: C, 64.41; H, 8.78; Found: C, 64.86; H, 8.93.

[0212]5 wt % of the DECH in BDDGE/PTHF (80/20) dissolved by heating itat 80-85° C. for 20 min. By including DECH, the DECH/BDDGE/PTHF mixtureis more reactive than BDDGE/PTHF (80/20) alone in parallel mixes with orwithout EDMAB. 5 wt % of the DECH in bis(epoxycyclopentyl ether) (BECPE)dissolved by heating it to 60° C. The mixture was more reactive thanBECPE alone (induction time: 35 sec. vs. 56 sec.; peak max time: 77 sec.vs. 128 sec.) in parallel mixes with EDMAB. The mixtures were much lessreactive without EDMAB (not complete with 20 min. irradiation). 10 wt %of the DECH in BECPE dissolved by heating it at 80-85° C. for 40 min.This mixture was more reactive than the above mixtures, which onlycontained 5 wt % DECH. The induction time was 23 sec. The peak max timewas 47 sec. EDMAB was used.

[0213] The synthesis scheme for making DECHE is shown below:

EXAMPLE 127,26-DIOXATRISPIRO[BICYCLO[4.1.0]HEPTANE-4,5′-1,3-DIOXANE-2′,2″-1,3-DIOXANE-5″,3′″-BICYCLO[4.1.0]HEPTANE(DCHE)

[0214](5,6:16,17-diepoxy-1,10,12,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane)

[0215] The synthetic sequence employed in the preparation of this epoxyspiroorthocarbonate is set forth in the following synthesis schemes.

[0216] 8,10,19,20-Tetraoxatrispiro [5.2.2.5.2.2]henicosa-2,14-diene (DCH2)

[0217] To a three-necked round-bottomed flask, equipped with aDean-Stark trap (20 mL), a reflux condenser, a thermometer and amagnetic stir bar, was placed 2,2-cyclohexene-dimethanol 1 (15.78 g, 111mmol) and 400 mL of toluene under an atmosphere of N₂. The mixture wasbrought to reflux and maintained at reflux temperature for 2 hours toazeotropically remove any moisture. About 100 mL (5×20 mL) of azeotropicmixture was collected in the Dean-Stark trap. The mixture was thenallowed to slowly cool to room temperature and 0.3 g of anhydrouspara-toluenesulfonic acid (PTSA) was added, followed by dropwiseaddition of tetraethylorthocarbonate (TEOC, 11.7 mL, 56 mmol). Theresulting mixture was brought to reflux to azeotropically remove ethanolgenerated during the reaction. The azeotropic mixture was shaken withsalt water to determine the amount (volume) of ethanol collected. Thereaction was monitored by GC (5 min at 105° C., a 20° C./min rise to225° C.) and/or by TLC (silica gel, 15% ether/hexanes). After a total of160 m L of azeotropic mixture (12.3 mL of ethanol) was collected, thereaction mixture was allowed to reflux for an additional 2 hours andthen allowed to stir at 102° C. overnight. The reaction mixture wasallowed to slowly cool to room temperature and then neutralized by theaddition of 1 mL of triethylamine. The resulting mixture was allowed tostir at room temperature for an additional 30 min, dried over anhydrousmagnesium sulfate, filtered and concentrated under reduced pressure togive a light yellowish solid. The crude material was then purified byflash chromatography (silica gel, 15-25% ether/hexanes) or byrecrystallization from refluxing ethyl ether/hexanes (v/v 1:1). Thedesired product8,10,19,20-tetraoxatrispiro[5.2.2.5.2.2]henicosa-2,14-diene 2 (DCH) wasobtained as white crystals in 80% yield. Mp (DSC) 118° C.; ¹H-NMR(CDCl₃, 300 MHz) δ 126.20, 124.29, 114.82, 70.21, 30.62, 26.56, 21.42;IR (KBr pellet) (cm⁻¹) 3020, 2920, 2850, 1630, 1440, 1365, 1250, 1225,1190, 1100, 1025, 1000, 935, 920, 650; Anal. Calcd for C₁₆H₂₆O₅: C,69.84; H, 8.27; Found: C, 69.68; H, 8.42.

7,26-Dioxatrisprio[bicyclo[4.1.0]heptane-4,5′-1,3-dioxane-2′,2″-1,3-dioxane-5″,3″-bicyclo[4.1.0]heptane(DCHE 3)

[0218](5,6:16,17-Diepoxy-1,10,12,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane)

[0219] The spiroorthocarbonate 3 was prepared employing the biphasicepoxidation procedure described by Anderson and Veysoglu due to the acidsensitive nature of this class of compounds. To a round-bottomed flaskwas placed a solution of8,10,19,20-tetraoxatrispiro[5.2.2.5.2.2]henicosa-2,14-diene 2 (DCH-TOSU,5.0 g, 17.1 mmol) in 250 mL of methylene chloride (CH₂Cl₂). To thissolution was added 0.5 M aqueous solution of sodium bicarbonate (105 mL,pH ˜8). The resulting biphasic mixture was stirred vigorously at roomtemperature and then m-chloroperbenzoic acid (57-86% mCPBA, 5.44 g,˜34.54 mmol) was slowly added in several portions over a period of 20minutes. The resulting mixture was allowed to stir for 5 hours at roomtemperature and the reaction progress was monitored by TLC (silica gel,25% ether/hexanes). The two phases were separated and the organic phasewas washed successively with 1 N aqueous NaOH (2×75 mL) and water (2×75mL). The organic phases were combined, dried over anhydrous Na₂SO₄, andconcentrated under reduced pressure to give an off-white solid. Thecrude material was washed with 5 mL of cold ether (pre-cooled at 0° C.)and recrystallized two times from diethyl ether. The desired productDCHE 3 was obtained as white crystals in 90% yield. Mp (DSC) 184.65° C.;¹H-NMR (CDCl₃, 300 MHz, mixture of diastereomers) δ 3.70-3.44 (m, 8H),3.16-3.04 (m, 4H), 2.12-1.15 (m, 12H); ¹³C-NMR (CDCl₃, 300 MHz, mixtureof diastereomers) δ 114.34, 114.30, 71.71, 71.59, 71.47, 71.36, 69.11,68.99, 68.95, 51.56, 50,05, 29.37, 29.32, 29.29, 29.23, 22.74, 19.82,19.78; IR (KBr pellet) (cm⁻¹) 2920, 1440, 1365, 1250, 1225, 1200, 1100,1000, 930, 860, 800, 780; Anal. Calcd for C₁₇H₂₄O₆: C, 62.95; H, 7.46;Found: C, 62.49; H, 7.26.

[0220] The synthesis scheme for making DCHE is shown below:

EXAMPLE 135,5-DIETHYL-18-OXADISPIRO[1,3-DIOXANE-2,2′-1,3-DIOXANE-5′,3″BICYCLO[3.1.0]HEXANE](DECPE)

[0221](11,11-Diethyl-2,3-epoxy-7,9,13,14-tetraoxadispiro[4.2.5.2]pentadecane)

[0222](3,3-Diethyl-11,12-epoxy-1,5,7,15-tetraoxadispiro[5.2.4.2]pentadecane)

[0223] The synthetic sequence employed in the preparation of this epoxyspiroorthocarbonate is set forth in the following synthesis schemes.

[0224] 5,5-Diethyl-1,3-dioxane-2-thione(1)

[0225] The thiocarbonate 1 was prepared in a variation of thethiocarbonylation procedure developed by Corey and Hopkins. To athree-necked round-bottomed flask, equipped with a mechanical stirrerand an additional funnel, was placed 2,2-diethyl-1,3-propanediol (15.86g, 120 mmol), 4-dimethylaminopyridine (DMAP, 29.32 g, 240 mmol) and 120mL of toluene under an atmosphere of nitrogen. The mixture was allowedto stir at room temperature until a homogeneous solution was reached.The mixture was cooled to 0-5° C. and then a solution of thiophosgene(9.43 mL, 20 mmol) in 90 mL of toluene was added dropwise via theadditional funnel over a period of 90 min. This resulted in theformation of a bright orange DMAP-thiophosgene complex. After thecompletion of addition, the reaction mixture was allowed to stir for anhour at 0-5° C. and then slowly warmed to room temperature. The reactionmixture was allowed to stir at room temperature for an additional hourand then the precipitated DMAP-HCl salt was removed by filtration. Thefiltrate was concentrated under reduced pressure using a rotaryevaporator. The crude material was purified by recrystallization (thecrude material was dissolved in refluxing ether, allowed to cool to roomtemperature and slowly evaporated) or by column chromatography (silicagel, 2:1 methylene chloride/hexanes). The desired thiocarbonate 1 wasobtained as white crystalline in 70% yield. Mp (DSC) 64.4° C.; ¹1.-NMR(CDCl₃, 300 MHz) δ 4.17 (s, 4H), 1.51-1.43 (q, 4H, J=7.5 Hz), 0.92-0.87(t, 6H, J=7.5 Hz); ¹³C-NMR (CDCl₃, 300 MHz) δ 189.53, 76.08, 33.67,23.09, 6.97; IR (Kbr pellet) cm⁻¹) 2960, 2920, 1455, 1395, 1380, 1290,1240, 1200, 1180, 1060, 990, 930, 720.

[0226] Methyl 1-(Methoxycarbonyl)cyclopent-3-enecarboxylate (2)

[0227] (Dimethyl 3-Cyclopentene-1,1-dicarboxylate)

[0228] The dimethyl diester 2 was prepared employing Depres and Greene'sprocedure. To a flame dried round-bottomed flask was placed dimethylmalonate (ACROS, 99+%, 26.7 g, 23.1 mL, 200 mmol) and anhydrousdimethylformamide (DMF, 300 mL). The mixture was cooled to 0° C. underan atmosphere of nitrogen while stirring. To this solution was thenadded lithium hydride (ACROS, 98%, 4.06 g, 500 mmol) powder in oneportion. The resulting mixture was allowed to stir at 0° C. until theevolution of hydrogen ceased (˜3 hours). To this heterogeneous mixturewas then slowly added cis-1,4-dichloro-2-butene (ACROS, 95%, 30 g, 25.3mL, 228 mmol). The resulting mixture was allowed to slowly come to roomtemperature and then allowed to stir for 72 hours (the color of theheterogeneous mixture changed from white to brown overnight). Thereaction progress was monitored by TLC (silica gel, 20% ethylether/hexanes). The reaction mixture was diluted with 20% ethylether/hexanes (500 mL) and the solution poured into cold water (350 mL).The organic phase was separated, washed successively with water (300 mL)and brine (300 mL), dried over anhydrous sodium sulfate and concentratedunder reduced pressure to give a light yellow solid. The crude materialwas recrystallized from refluxing hexanes (or ethyl ether). The desireddimethyl diester 2 was obtained as white needles in 50% yield. Mp (DSC)63.48° C., 1H-NMR (CD₁₃, 300 MHz) δ 5.56 (s, 2H), 3.68 (2s, 6H), 2.97(s, 4H); ¹³C-NMR (CDCl₃, 300 MHz) δ 172.47, 127.64, 58.60, 52.66, 40.78;FT-IR (CH₂Cl₂) (cm⁻¹) 3061, 2955, 1733, 1624, 1436, 1266, 1076, 975.

[0229] [1-(Hydroxymethyl)cyclopent-3-enyl]methan-1-ol (3)

[0230] (1,1-Bis(hydroxymethyl)-3-cyclopenene)

[0231] The desired diol was prepared via LAH reduction of thecorresponding diester 2. To a flame dried round-bottomed flask wasplaced lithium aluminum hydride (LAH, Aldrich, 95%, 6.99 g, 175 mmol)and anhydrous tetrahydrofuran (TUF, 235 mL). The resulting suspensionwas cooled to 0° C. and then a solution of the dimethyl diester 2 in 58mL of anhydrous THF was added dropwise via an additional funnel. Theresulting mixture was allowed to stir at 0° C. for 4 hours whilemonitored by TLC. The reaction mixture was then carefully quenched bysequential addition of 6 mL of water, 6 mL of 3 N aqueous solution ofNaOH and 17.5 mL of water. The resulting mixture was allowed to slowlycome to room temperature and then filtered through a bed of celite. Theresultant solid cake was washed repeatedly with refluxing THF (total of250 mL). The filtrate was dried over anhydrous sodium sulfate andconcentrated under reduced pressure to afford alight yellow oil whichwas dissolved in 10 mL of refluxing toluene and the water wasazeotropically removed. removal of the remaining toluene gave anoff-white solid, which was recrystallized from refluxing toluene. Thedesired diol 3 was obtained as white needles in 86.2% yield, Mp (DSC)81.21° C.; 1H-NMR (CD₁₃, 300 MHz) δ 5.59 (s, 2H), 3.73 (s, 2H), 3.63 (s,4H), 2.16 (s, 4H); ^(—C-NMR (CD) ₁₃, 300 MHz) δ 128.69, 69.19, 47.53,38.61; FT-IR (CH₂Cl₂) (cm⁻¹) 3323, 3055, 2918, 2846, 1619, 1442, 1419,1357, 1266, 1114, 1093, 1025, 955, 909, 896.

[0232] 8,8-Dibutyl-7,9-dioxa-8-stannaspiro[4.5]dec-2-ene (4)

[0233] (3,3-Dibutyl-2,4-dioxa-3-stannaspiro[5.4]dec-8-ene)

[0234] The tin adduct 4 and DECP 5 were prepared employing theprocedures developed by Stansbury and Bailey. To a three-neckedround-bottomed flask, equipped with a thermometer, a reflux condenserand a Dean-Stark trap with an extension condenser, was placed aheterogeneous mixture of[1-hydroxymethyl)cyclopent-3-enyl]methan-1-ol(3,7.73 g, 60.3 mmol) anddibutyltin oxide (Aldrich, 98%, 15.32 g, 60.3 mmol) in 250 mL oftoluene. The mixture was brought to reflux and became clear solution.The reaction mixture was allowed to reflux for 3 hours while theliberated water was collected (with toluene) in the Dean-Stark trap(5×20 mL of the azeotropic mixture was collected). The Dean-Stark trapwas removed and the reaction mixture was then allowed to reflux foradditional 2 hours and then slowly cooled to room temperature under anatmosphere of nitrogen. The8,8-dibutyl-7,9-dioxa-8-stannaspiro[4.5]undec-2-ene 4 thus generated insitu was subjected to the subsequent reaction without furtherpurification.

[0235] 11,11-Diethyl-7,9,13,14-tetraoxadispiro[4.2.5.2]pentadec-2-ene(DECP 5)

[0236] (3,3-Diethyl-1,5,7,15-tetraoxadispiro[5.2.4.2]pentadec-11-ene)

[0237] To the above solution of8,8-dibutyl-7,9-dioxa-8-stannaspiro[4.5]dec-2-ene 4 was added5,5-diethyl-1,3-dioxane-2-thione 1 (10.1 g, 60.3 mmol) in several smallportions at room temperature over a period of 20 min. The resultingmixture was allowed to stir at room temperature for 24 hours. Thereaction was monitored by TLC (silica gel, 25% ether/hexanes). Thereaction mixture was then concentrated under reduced pressure and theresidue taken up with ethyl ether (white suspension formed uponstanding). The ether solution was filtered and concentrated underreduced pressure to give light yellowish oil. The crude material waspurified by column chromatography (silica gel, 10-15% ethylether/hexanes). The desired11,11-diethyl-7,9,13,14-tetraoxadispiro[4.2.5.2]pentadec-1-ene (DECP 5)was obtained as white solid in 72% yield. Mp (DSC) 95.19° C., ¹H-NMR(CD₁₃, 300 MHz) δ 5.60 (s, 2H), 3.80 (s, 4H), 3.69 (s, 4H), 2.27 (s,4H), 1.45-1.37 (q, 4H, J=7.8 Hz), 0.82-0.77 (t, 6H, J-7.8 Hz); ¹³C-NMR(CD₁₃, 300 Mhz) δ 128.52 114.39, 71.04, 69.48, 39.76, 34.33, 23.16,7.12; FT-IR (Kbr pellet) (cm⁻¹) 3053, 2968, 1619, 1457, 1360, 1266,1212, 1178, 1001, 938; Anal. Calcd for C1H₂₄O4: C, 67.14; H, 901; Found:C, 67.44; H, 9.22.

[0238]5,5-Diethyl-18-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′3″-bicyclo[3.1.0]hexane](DECPE 6)

[0239](11,11-Diethyl-2,3-epoxy-7,9,13,14,-tetraoxadispiro[4.2.5.2]pentadecane)

[0240](3,3-Diethyl-11,12-epoxy-1,5,7,15-tetroxadispiro[5.2.4.2]pentadecane)

[0241] The spiroorthocarbonate 6 was prepared employing the biphasicepoxidation procedure described by Anderson and Veysoglu due to the acidsensitive nature of this class of compounds. To a round-bottomed flaskwas placed11,11-diethyl-7,9,13,14-tetraoxadispiro[4.2.5.2]pentadec-1-ene (DECP 5,2.65 g, 9.88 mmol) and 130 mL of methylene chloride (CH₂Cl₂). To thissolution was added 0.5 M aqueous solution of sodium bicarbonate (3 mL,pH ˜8). The resulting biphasic mixture was allowed to stir vigorously atroom temperature and then mchloroperenzoic acid (Aldrich, 57.86% mCPBA,2.74 g, ˜10.87 mmol) was slowly added in several portions over a periodof 30 minutes. The resulting mixture was allowed to stir overnight atroom temperature and the reaction progress was monitored by TLC (silicagel, 50% ether/hexanes). The two phases were separated and the organicphase was washed successively with 1 N aqueous NaOH (2×100 mL) and water(2×75 mL). The organic phases were combined, dried over anhydrousNa₂SO₄, and concentrated under reduced pressure to give an off-whitesolid. The crude material was washed with 5 mL of cold ether (pre-cooledat 0° C.) and purified by flash chromatography (silica gel, 50% ethylether/hexanes) or by recrystallization two times from hexanes (the crudematerial was dissolved in refluxing hexanes, allowed to cool to roomtemperature and slow evaporization ). The desired produce DECPE 6 wasobtained as white crystals in 81% yield. Mp (DSC) 93.16° C. 1H-NMR(CD₁₃, 300 MHz) δ 3.76-3.67 (3s, 8H), 3.50 (s, 2H), 2.14-2.09 (d, 2H,J=7.5 Hz), 1.58-1.54 (d, 2H, J-15 Hz), 1.44-1.36 (q, 4H, J=7.5 Hz),0.82-0.77 (t, 6H, J=7.5 Hz); ¹³C-NMR (CD₁₃, 300 MHz) δ 114.24, 72.31,71.27, 69.51, 57.61, 38.56, 34.81, 34.36, 23.17, 7.13; FT-IR (Kbrpellet) (cm⁻¹) 2968, 1483, 1460, 1422, 1365, 1266, 1255, 1221, 1205,1181, 1110, 1060, 1024, 1004, 870, 837, 795, 762, 744; Anal. Calcd forC₁₅H₂₄O₅: C, 63.36; H, 8.51; Found: C, 63.60; H, 8.75.

[0242] The synthesis scheme for making DECPE is shown below:

EXAMPLE 146,24-DIOXATRISPIRO[BICYCLO[3.1.0]HEXANE-3,5′-1,3-DIOXANE-2′2″-1,3-DIOXANE-5″3′″-BICYCLO[3.1.0]HEXANE(DCPE)

[0243] The synthetic sequence employed in the preparation of this epoxyspiroorthocarbonate is set forth in the following synthesis schemes.

[0244] Methyl 1-(Methoxycarbonyl)cyclopent-3-enecarboxylate (1)

[0245] (Dimethyl 3-Cyclopentene-1,1-dicarboxylate)

[0246] The dimethyl diester 1 was prepared employing Deprés and Greene'sprocedure. To a flame dried round-bottomed flask was placed dimethylmalonate (ACROS, 99+%, 26.7 g, 23.1 mL, 200 mmol) and anhydrousdimethylformamid (DMF, 300 mL). The mixture was cooled to 0° C. under anatmosphere of nitrogen while stirring. To this solution was then addedlithium hydride (ACROS, 98%, 4.06 g, 500 mmol) powder in one portion.The resulting mixture was allowed to stir at 0° C. until the evolutionof hydrogen ceased (˜3 hours). To this heterogeneous mixture was thenslowly added cis-1,4-dichloro-2-butene (ACROS, 95%, 30 g, 25.3 mL, 228mmol). The resulting mixture was allowed to slowly come to roomtemperature and then allowed to stir for 72 hours (the color of theheterogeneous mixture changed from white to brown overnight). Thereaction progress was monitored by TLC (silica gel, 20% ethylether/hexanes). The reaction mixture was diluted with 20% ethylether/hexanes (500 mL) and the solution poured into cold water (350 mL).The organic phase was separated, washed successively with water (300 mL)and brine (300 mL), dried over anhydrous sodium sulfate and concentratedunder reduced pressure to give a light yellow solid. The crude materialwas recrystallized from refluxing hexanes (or ethyl ether). The desireddimethyl diester 1 was obtained as white needles in 50% yield. Mp (DSC)63.48° C.; ¹H-NMR (CDCl₃, 300 MHz) δ 5.56 (s, 2H), 3.68 (2s, 6H), 2.97(s, 4H); ¹³C-NMR (CDCl₃, 300 MHz) δ 172.47, 127.64, 58.60, 52.66, 40.78;FT-IR (CH²Cl²) (cm⁻¹) 3061, 2955, 1733, 1624, 1436, 1266, 1076, 975.

[0247] [1-(Hydroxymethyl)cyclopent-3-enyl]methan-1-ol (2)

[0248] (1,1-Bis(hydroxymethyl)-3-cyclopentene)

[0249] The desired diol 2 was prepared via LAH reduction of thecorresponding diester 1. To a flame dried round-bottomed flask wasplaced lithium aluminum hydride (LAH, Aldrich 95%, 6.99 g, 175 mmol) andanhydrous tetrahydrofuran (THF, 235 mL). The resulting suspension wascooled to 0° C. and then a solution of the dimethyl diester 1 in 58 mLof anhydrous THF was added dropwise via an additional funnel. Theresulting mixture was allowed to stir at ° C. for 4 hours whilemonitored by TLC. The reaction mixture was then carefully quenced bysequential addition of 6 mL of water, 6 mL of 3 N aqueous solution ofNaOH and 17.5 mL of water. The resulting mixture was allowed to slowlycome to room temperature and then filtered through a bed of Celite. Theresultant solid cake was washed repeatedly with refluxing THF (total of250 mL). The filtrate was dried over anhydrous sodium sulfate andconcentrated under reduced pressure to afford a light yellow oil whichwas dissolved in 150 mL of refluxing toluene and the water wasazeotropically removed. Removal of the remaining toluene gave anoff-white solid, which was recrystallized from refluxing toluene. Thedesired diol 2 was obtained as white needles in 86.2% yield. Mp (DSC)81.21° C., ¹H-NMR (CDCl₃, 300 MHz) δ 5.59 (s, 2H), 3.73 (s, 2H), 3.63(s, 4H), 2.16 (S, 4H); ^(—)C-NMR (CDCl₃, 300 MHz) δ 128.69, 69.19,47.53, 38.61; FT-IR (CH₂Cl₂) (cm⁻¹) 3323, 3055, 2918, 2846, 1619, 1442,1419, 1357, 1266 1114, 1093, 1025, 955, 909, 896.

[0250] 7,9,17,18-Tetraoxatrispiro[4.2.2.4.2.2]nonadeca-2,13-diene (DCP3)

[0251] To a three-necked round-bottomed flask, equipped with aDean-Stark trap (20 mL), a reflux condenser, a thermometer and amagnetic stir bar, was placed diol 1 (14.8 g, 115.5 mmol) and 370 mL oftoluene under an atmosphere of N₂. The mixture was brought to reflux andmaintained at reflux temperature for 2 hours to azeotropically removeany moisture. About 100 mL (5×20 mL) of azeotropic mixture was collectedin the Dean-Stark trap. The mixture was then allowed to slowly cool toroom temperature and 0.2 g of anhydrous para-toluenesulfonic acid (PTSA)was added, followed by dropwise addition of tetraethylorthocarbonate(TEOC, 4563-91-2, 99.1%, 12.2 mL, 57.8 mmol). The resulting mixture wasbrought to reflux to azeotropically remove ethanol generated during thisreaction. The azeotropic mixture was shaken with sale water to determinethe amount (volume) of ethanol collected. After a total of 140 mL ofazeotropic mixture (12.5 mL of ethanol) was collected, the reactionmixture was allowed to reflux for an additional 2 hours and then allowedto stir at 102° C. overnight. The reaction mixture was allowed to slowlycool to room temperature and then neutralized by the addition of 1 mL oftriethylamine. The resulting mixture was allowed to stir at roomtemperature for an additional 30 min, and was stripped off solvents togive an off white solid. The crude material was then purified by flashchromatography (silica gel, CH₂Cl₂/hexanes 2/1 v/v) or byrecrystallization from refluxing toluene. The desired product7,9,17,18-tetraoxatrispiro[4.2.2.4.2.2]nonadeca-2,13-diene (DCP 3) wasobtained as white crystals in 62% yield. Mp (DSC) 174.53° C.; ¹H-NMR(CDCl₃, 300 MHz) δ 5.61 (s, 2H), 3.82 (s, 4H), 2.29 (s, 4H); ¹³C-NMR(CDCl₃, 300 MHz) δ 128.53, 114.14, 71.07, 39.79; FT-IR (CH₂Cl₂) (cm-1)3052, 2947, 2928, 2880, 2842, 1614, 1481, 1267, 1210, 1171, 1014, 990,738, 671; Anal. Calcd for C₁₅H₂₀O₄: C, 68.16; H, 763; Found: C, 68.18;H, 7.81.

[0252]6,24-Dioxatrispiro[bicyclo[3.1.0]hexane-3-5′-1,3-dioxane-2′2″-1,3-dioxane-5″3′″-bicyclo[3.1.0]hexane](DCPE 4)

[0253] The spiroorthocarbonate 4 was prepared employing the biphasicepoxidation procedure described by Anderson and Vesoglu due to the acidsensitive nature of this class of compounds. To a round-bottomed flaskwas placed a solution of7,9,17,18-tetraoxatrispiro[4.2.2.4.2.2]nonadeca-2,13-diene (DCP 3, 4.3g, 16.27 mmol) in 215 mL of methylene chloride (CH₂Cl₂). To thissolution was added 0.5 M aqueous solution of sodium bicarbonate (113 mL,pH ˜8). The resulting biphasic mixture was allowed to stir vigorously atroom temperature and then m-chloroperbenzoic acid (Aldrich, 57-86%mCPBA, 8.6 g, ˜35.8 mmol) was slowly added in several portions over aperiod of 20 minutes. The resulting mixture was allowed to stirovernight at room temperature and the reaction progress was monitored byTLC (silica gel, 95% CH₂Cl₂/Et₂O, v/v). The two phases were separatedand the organic phase was washed successively with 1 N aqueous NaOH(2×150 mL) and water (2×100 mL). The aqueous phase was back extractedwith 100 mL CH₂Cl₂. The organic phases were combined, dried overanhydrous Na₂SO₄, and concentrated under reduced pressure to give anoff-white solid. The crude material was purified by flash chromatography(silica gel, 95% CH₂Cl₂/Et₂O, v/v). The desired produce DCPE 4 wasobtained as white crystals in 75% yield. Mp (DSC) 256.55° C. ¹H-NMR(CD₁₃, 300 MHz) δ 3.75-3.68 (m, 8H), 3.50 (s, 4H), 2.14-2.08 (dd, 4H,J=153 Hz), 1.58-1.53 (d, 4H, J-15 Hz); ^(—)C-NMR (CD₁₃, 300 MHz) δ113.76, 72.33, 71.29, 57.59, 38.54, 34.84, 34.75; FT-IR (CH₂Cl₂) (cm-1)3012, 2945, 1486, 1434, 1266, 1210, 1105, 1047, 1019, 991, 830, 739;Anal. Calcd for C₁₅H₂₄O₅: C, 60.80; H, 6.80; Found: C, 60.55; H, 6.97.

[0254] The synthesis scheme for making DCPE is shown below:

[0255] The photopolymerizable compositions of the invention are preparedby simply admixing, under “safe light” conditions, the components of theinventive compositions. Suitable inert solvents may be employed ifdesired when effecting this mixture. Any solvent may be used which doesnot react appreciably with the components of the inventive compositionsand which does not substantially interfere with cationic cure of thecomposition at or below body temperature. Examples of suitable solventsinclude acetone, dichloromethane, and acetonitrile. A liquid material tobe polymerized (at body temperature or less, if desired) may be used asa solvent for another liquid or solid material to be polymerized.Solventless compositions can be prepared by simply dissolving thearomatic iodonium complex salt, sensitizer, and donor in the vinyl etherbased system with or without the use of mild heating to facilitatedissolution.

[0256] The compositions of the present invention provide a very usefulcombination of cure speed, cure depth and shelf life. They cure welleven when loaded with large amounts of fillers, and can be used in avariety of applications including graphic arts imaging (e.g. for colorproofing systems, curable inks, or silverless imaging), printing plates(e.g. projection plates or laser plates), photoresists, solder masks,electronic conformal coatings, coated abrasives, magnetic media,photocurable adhesives (e.g. for orthodontics) and photocurablecomposites (e.g., for autobody repair or dentistry).

[0257] The effectiveness of the vinyl ether/photoinitiator system of thepresent invention is illustrated by the following tables and examples.Tables 1 and 2 show that the time for polymerization of a vinyl ether isfaster when a ternary photoinitiator system is included.

[0258] For the experiments reported in Table 1, 98.0 wt % ethyleneglycol divinyl ether (EGDVE), 1.5 wt % (4-octyloxyphenyl) phenyliodoniumhexafluoroantimonate (OPIA), and 0.5 wt % camphorquinone (CQ) werecombined to make a resin. Various amounts of various electron donorcompounds were added to the resin, as shown in Table 1. The resin wascured at 37° C. and at wavelengths greater than 418 nm for 20 minutes oruntil the reaction stopped (ca. 9 mW/cm², 11 mg sample size, 40 ccN₂/min). The results shown in Table 1 indicated that the preferred donorcompounds are ethyl 4-(dimethylamino) benzoate (EDMAB),4-dimethylaminobenzoic acid (4-DMABA), 3-dimethylaminobenzoic acid(3-DMABA), 4-dimethylaminobenzoin (DMAB), N-phenylglycine (NPG),1,2,4-trimethoxybenzene (TMB), and 4-dimethylaminobenzaldehyde (DMABAL).EDMAB at 0.53 wt % resulted in an unresolved bimodal reaction exothermprofile. The first peak was the major peak, and the peak maxium time inTable 1 for this entry corresponds to this peak. 4-(Dimethylamino)phenethanol (4-DMAPE) at 0.1 wt % resulted in a baseline-resolvedbimodal endotherm profile. The second peak reached a slightly higherheat flow value than the earlier peak. The peak maximum time in Table 1for this entry corresponds to the second peak. TABLE 1 COMPARISON OF THEPOLYMERIZATION OF A VINYL ETHER WITH VARIOUS ELECTRON DONOR COMPOUNDSAND WITHOUT A ELECTRON DONOR COMPOUND Induction Photoinduced Reaction Wt% Added to Time Time to Exotherm Enthalpy Potential Promotor 1 GramResin (sec) Peak Max. (sec) ΔH (J/g) (mV) None 0.00 156 213 38 −25 Ethyl4-(dimethylamino) 0.53 11 13 161 200 benzoate (EDMAB) Ethyl4-(dimethylamino) benzoate 0.37 11 16 436 200 (EDMAB) Ethyl4-(dimethylamino) benzoate 0.10 10 13 434 200 (EDMAB)4-Dimethylaminobenzoic acid 0.10 15 22 513 184 (4-DMABA) 3-Dimethylaminobenzoic acid 0.10 19 30 382 115 (3-DMABA) 1,2,4-Trimethoxybenzene 0.1011 27 215 233 (TMB) 4-Dimethylaminobenzoin 0.10 22 73 450 261 (DMAB)N-phenylglycine 0.10 12 19 348 161 (NPG) 4-Dimethylaminobenzaldehyde0.10 16 27 495 245 (DMABAL) 4-(Dimethylamino) phenethanol 0.10 38 280480 17 (4-DMAPE) N,N-dimethylaniline 0.10 28 48 180 54 (DMA)Triethanolamine 0.10 91 109 10 −162 (TEA)

[0259] The data in Table 1 shows significant rate enhancement with theuse of certain electron donors in the system and inhibition may occurwith others. The data further shows that the use of too much electrondonor can slow the reaction rate.

[0260] For the experiments reported in Table 2, the photopolymerizationof various vinyl ethers with and without the use of an electron donor topromote the reaction are reported. Data showing runs where EDMAB wasused to promote the reaction are shown in parentheses after the numberscorresponding to runs without EDMAB. These results show using anelectron donor compound, such as EDMAB, can promote polymerization ofthe various vinyl ethers and decrease the induction time and the time tothe reaction's peak maximum relative to compositions not having anelectron donor. TABLE 2 VINYL ETHER HOMOPOLYMERIZATION PDSC VinylEnthalpy Induction Time to Conversion Enthalpy Rate Constant Ether (J/g)Time (sec) Max. (sec) at Max. (%) (kcal/mole eq) k (1/min) EGDVE 473(371)  52 (12)  89 (14) 50 (18)  6.45 (5.06)  3.6 (10.6) DEGDVE 539(33)   58 (37)  121 (113) 44 (30) 10.44 (6.39)  1.3 (1.40) TEGDVE 417(526)  59 (17)  70 (20) 13 (19) 10.07 (12.70) 2.1 (11.1) HDDVE 537 (451) 80 (51) 139 (58) 61 (23)  9.25 (7.77)  1.4 (15.5) CHDMDVE 330 (145) 123(30) 204 (76) 57 (24)  7.74 (3.40)  0.5 (2.8)  GVE 797 (429)  78 (56) 284 (242) 48 (51)  9.53 (5.13)  1.1 (0.8)  CEVE ND — — — — — POMDO ND —— — — — BDVE 370 (371) 381 (103) 537 (176) 34 (45) 10.27 (10.30) 1.1(3.6) 

[0261] Table 3 also shows the effects of curing various vinyl ethercompositions with and without an electron donor compound. The data showsthat reaction rates are faster when an electron donor compound is used.TABLE 3 PDSC PARAMETERS OF TEGDVE/ERL 4206 BASED MIXTURES CURED USING UVLIGHT, OR VISIBLE LIGHT WITH AND WITHOUT ELECTRON DONOR COMPOUND (EDMAB)H_(photo) (J/g) Induction Time (sec) Time to Max. (sec) Conversion atMax. (%) Component (Mole %) UV^(a) VIS^(b) VIS + E^(c) UV^(a) VIS^(b)VIS + E^(c) UV^(a) VIS^(b) VIS + E^(c) UV^(a) VIS^(b) VIS + E^(c) ERL4206 (50) 642 590 600 7 169 30 9 562 86 14 59 17 TEGDVE (50) ERL4206(45) 400 507 494 6 191 27 10 324 60 19 22 8 TEGDVE (45) PTHF (10)ERL4206 (45) 431 461 416 14 369 34 21 855 90 25 56 15 TEGDVE (45) SOCDEDPM (10) ERL 4206 (40.5) 364 378 362 12 328 38 19 577 79 25 30 17TEGDVE (40.5) PTHF (9.0) SOC DEDPM (10.0)

[0262] Examples 15, 16 and 17 further illustrate the importance ofincluding an electron donor compound in the present invention. Theseexamples show the variation in gel time when an electron donor compoundis included compared with when no donor compound is included.

EXAMPLE 15 Ternary Photoinitiator System for Curing Vinyl Ether ResinCompositions

[0263] A stock solution (“SL1”) of a vinyl ether mixture was prepared bycombining 15 grams of VECTOMER 2020 (Allied Signal) and 15 gramsVECTOMER 4010 (Allied Signal) and stirring until homogeneous.

[0264] Two photoinitiator systems were evaluated in SL1 for cure speed.Two compositions were prepared as follows: Composition A SL1 9.80 gCamphorquinone 0.05 g Diphenyliodonium hexafluoroantimonate 0.15 gComposition B SL1 9.80 g Camphorquinone 0.05 g Diphenyliodoniumhexafluoroantimonate 0.15 g 4-Dimethylaminobenzoic acid 0.05 g

[0265] Each composition was prepared by combining the ingredients atroom temperature and stirring until homogeneous. Samples were evaluatedfor cure speed according to the following procedure. Previously preparedmolds made from 2-mm thick “Teflon” sheet with a 4-mm diameter holethrough the sheet were clamped to a square of clear polyester film. Thehole was filled with a vinyl ether composition and then irradiated at adistance of 10 mm with a Visilux 2 (3M) dental curing light. The lightsource provided approximately 300-400 mw/cm² of energy between 400 and500 nanometers. Irradiation continued for 120 seconds or until a soft orhard gel was formed. Results are reported below. Composition Donor GelTime A None No Cure B DMABA 50 seconds

[0266] The data illustrates that a vinyl ether composition can berapidly photopolymerized when the electron donor 4-dimethylaminobenzoicacid (DMABA) is used in combination with the photosensitizercamphorquinone and proton source diphenyliodonium hexafluoroantimonate.No curing was observed in the absence of the donor DMABA.

EXAMPLE 16 Ternary Photoinitiator System for Curing Vinyl Ether ResinCompositions

[0267] Five photoinitiator systems were evaluated in the bishydroxybutyl vinyl ether isophthalate; (VECTOMER 4010 (Allied Signal))for cure speed. Five compositions were prepared as follows: CompositionA VECTOMER 4010 9.80 g Camphorquinone 0.05 g Diphenyliodoniumhexafluoroantimonate 0.15 g Composition B VECTOMER 4010 9.80 gCamphorquinone 0.05 g Diphenyliodonium hexafluoroantimonate 0.15 g Ethy4-dimethylaminobenzoate (EDMAB) 0.05 g Composition C VECTOMER 4010 9.80g Camphorquinone 0.05 g Diphenyliodonium hexafluoroantimonate 0.15 g4-Dimethylaminobenzoic acid (DMABA) 0.05 g Composition D VECTOMER 40109.80 g Camphorquinone 0.05 g Diphenyliodonium hexafluoroantimonate 0.15g N-phenylglycine (NPG) 0.05 g Composition E VECTOMER 4010 9.80 gCamphorquinone 0.05 g Diphenyliodonium hexafluoroantimonate 0.15 gN,N-Dimethylaniline (DMA) 0.05 g

[0268] Each composition was prepared by combining the ingredients atroom temperature and stirring until homogeneous. Samples were evaluatedfor cure speed according to the procedure of Example 1. Results arereported below. Composition Donor Gel Time Comments A None 115 secslight surface cure B EDMAB  25 sec exotherm/color C DMABA  25 secexotherm D NPG  70 sec E DMA No cure

[0269] The data illustrates that the vinyl ether VECTOMER 4010 can berapidly photopolymerized when several low basicity electron donorcompounds are used in combination with the photosensitizercamphorquinone and proton source diphenyliodonium hexafluoroantimonate.Limited photocuring was observed in the absence of the electron donorsor in the presence of the higher basicity electron donor DMA.

EXAMPLE 17

[0270] A variety of visible light absorbing sensitizers were evaluatedin vinyl ether formulations containing approximately 1.50%diphenyliodonium hexafluoroantimonate (DPISbF₆), 0.50 sensitizercompound and optionally 0.50% EDMAB by weight. Solutions A and B withoutand with EDMAB respectively were prepared as shown below: IngredientParts by weight Solution A VECTOMER 4010 100.00 Diphenyliodoniumhexafluoroantimonate 1.50 Solution B VECTOMER 4010 100.00Diphenyliodonium hexafluoroantimonate 1.50 4-Dimethylaminobenzoic acid0.50

[0271] Sensitizers were evaluated by transferring 0.0020 grams of thesensitizer to a 2 dram glass vial followed by the addition of 2 dropsdichloromethane solvent and 1.0 grams of solution A. Compositions weremixed until homogeneous and evaluated for gel time as described below.One drop of each vinyl ether composition was applied to a clear 1 cm×1cm square of clear polyester film. Samples were irradiated with a “GELight Engine” (a white light source available from General Electric) oralternatively with a Visilux dental curing light (available from 3M),where indicated by an*in the table below. The samples were irradiated ata distance of about 5-6 centimeters and were probed to establish geltimes up to a maximum of 90 seconds. Samples were also examined forinitial color and any observable color change. The same procedure wasrepeated for solution B. Set out below are the sensitizer, the gel timeswith and without EDMAB and any key observations. Gel Time (seconds) WithSensitizer No EDMAB EDMAB Comments None No Cure No Cure CamphorquinoneNo Cure 20 Rose bengal No Cure 35 red to yellow Rose bengale No Cure 63red to yellow Acridine Orange 45 15 * Visilux light Malachite Green NoCure 55 Methylene Blue No Cure 43 blue to yellow Toluidine Blue 81 32blue to yellow Safranine O 25 11 * Visilux light orange to yellow4,5-dibromofluorescein 31 23 orange to yellow

[0272] Examples 15-17 show a variety of vinyl ether systems that containa ternary photoinitiator system. The data shows that use of an electrondonor as part of the ternary photoinitiator system shortens reactiontime. Still further, the data illustrates that an array of visible lightsensitizers, in combination with DPISbF₆ and the electron donor EDMAB,photocures faster than those formulations with sensitizer and DPISbF₆alone.

EXAMPLE 18

[0273] The effect of an electron donor compound on thephotohomopolymerization of selected vinyl ethers is further illustratedby the graph in FIG. 1. A*, B*, and C* show the photopolymerization ofcertain vinyl ethers containing 0.1 wt % of the electron donor compoundethyl 4-dimethylaminobenzoate (EDMAB). A, B, and C show thepolymerization of certain vinyl ethers with no electron donor compound.Specifically, A and A* show the effect of an electron donor compound onethylene glycol divinyl ether (EGDVE). B and B* show the effect of anelectron donor compound on tri(ethylene glycol) divinyl ether (TEGDVE).C and C* show the effect of an electron donor compound on hexanedioldivinyl ether (HDDVE). The OPIA/CQ equaled 0.25/0.5 mole % based onmoles of vinyl groups. The experiments illustrated in FIG. 1 wereperformed at 37° C., at wavelengths greater than 418 nm, and 11.6mW/cm².

[0274] A substantial amount of vinyl ether is used in all of thephotopolymerizable compositions of the present invention. The term“substantial amount of vinyl ether” means that of all the polymerizablecomponents in the composition, vinyl ether is present in the greatestamount. Thus, a composition that has a substantial amount of vinyl etheris predominately vinyl ether. Preferably, any matrix that is formed fromthe compositions of the present invention is primarily defined by vinylether.

[0275] The use of vinyl ether as the substantial component of theformulations of the present invention provides several advantages.Compositions that include a substantial amount of vinyl ether with anSOC provide a matrix for taking advantage of the potential volumeexpansion properties of SOCs. Because most SOCs are solids at roomtemperature and are polymerizable to any significant extent only atelevated temperatures over extended time periods, polymerized SOCsresult in polymers that have relatively poor physical properties. Bycreating mixtures of vinyl ethers, SOCs, and a photoinitiator system,polymerization can occur at room temperature. Data from thephotopolymerization of various vinyl ether/SOC compositions of thepresent invention is shown in Tables 4 and 5. TABLE 4 VE/TOSUPHOTOPOLYMERIZATION COMPOSITIONS AND RESULTS ΔH_(theory) ΔH_(EXPER)Reacted Ind. Time Peak Max ΔH_(exper) at No. VE TOSU Wt. % PI Wt. % RPWt. % (J/g) (J/g) (%) (sec) (sec) Max.(%) 1 TEGDVE DEDPM 25 CE1012 0.5 —— 438 392 89 91 137 16 2 TEGDVE DEDPM 25 CD1012 0.5 EDMAB 0.1 438 380 8729 33 18 3 TEGDVE DEDPM 25 RHO2074 0.5 — — 439 382 87 109 141 21 4TEGDVE DEDPM 25 RHO2074 0.5 EDMAB 0.1 439 393 90 31 37 22 5 TEGDVE DECHE25 CD1012 0.5 — — 516 348 67 130 235 35 6 TEGDVE DECHE 25 CD1012 0.5EDMAB 0.1 515 428 83 39 71 31 7 TEGDVE DTM 25 OPIA 0.5 — — 464 321 69 5091 8 8 GVE DEDPM 25 OPIA 0.5 — — 1139 221 19 207 754 61 9 GVE DECHE 25CD1012 0.5 — — 1218 210 17 117 366 34 10 GVE DECHE 25 CD1012 0.5 EDMAB0.1 1218 232 19 36 232 30 11 GVE DECHE 25 RHO2074 0.5 — — 1219 245 20170 558 45 12 GVE DTM 25 OPIA 0.5 — — 1139 94 8 177 479 37 13 HDDVEDEDPM 25 OPIA 0.5 — — 520 194 37 506 659 33 14 HDDVE DEDPM 25 OPIA 0.5EDMAB 0.1 520 498 96 30 46 14 15 HDDVE DECHE 25 CD1012 0.5 — — 600 — — —— — 16 HDDVE DM 25 CD1012 0.5 — — 520 — — — — —

[0276] Table 4 shows that when an electron donor, such as EDMAB, isused, the polymerization proceeds quicker and the polymer is morecompletely cured. This table further shows that certain vinyl ether/SOCcombinations are more reactive than others. TABLE 5 VE/TOSUPHOTOPOLYMERIZATE PRODUCTS Wt. No. Lost Description of Post PDSC Product1 0 Colorless clear elastomeric gel; no resistance to puncture 2 0.2Black center, dark brown, soft brittle disk 3 1.2 Dark brown center,yellow-brown flexible removable disk 4 0.2 Brown black brittle easilycrumbled disk 5 0 Elastomeric solid, tacky surface 6 0 Yellow, hard, canbe scratched 7 0 Cured hard, can be scratched 8 4.7 Soft elastomeric gel9 3.3 Brittle, crumbled easily 10 4.0 Brittle, crumbled easily 11 3.2Clear, brittle, easily crumbled, somewhat elastomeric 12 5.9 Skin ontop, still liquid below surface 13 1.1 Soft, semi-gel 14 0.6 Clear,tough, flexible, removable disk 15 0 Liquid, no change 16 0.1 Liquid, nochange

[0277] Table 5 includes data that shows that less weight is lost when anelectron donor is used in the composition, which indicates a morecomplete conversion of the reaction materials.

[0278] The vinyl ether/epoxide/polyol polymerizable composition of thepresent invention includes a substantial amount of vinyl ether. By usingan epoxide with a vinyl ether, the physical properties of the vinylether are improved. Data from the photopolymerization of various vinylether/epoxide/polyol compositions is shown in Tables 6A, 6B, and 6C. Thenumbers shown in parentheses show data where an electron donor waspresent. The reaction proceeded faster when an electron donor was used.TABLE 6A VINYL ETHER/DIEPOXIDE/POLYOL PHOTOPOLYMERIZATIONS: SERIES 1A(UVR6105) Enthalpy Induction Time to Conversion Enthalpy No. Vinyl Ether(J/g) Time (sec) Max. (sec) at Max (%) (kcal/mole eq) 17 EGDVE 230 137287 20  4.56 18 DEGDVE nc — — — — 19 TEGDVE 345 (353)  76 (16) 121 (33)12 (15)  9.55 (9.77) 20 HDDVE nc — — — — 21 CHDMDVE 189 106 184 24  5.1222 GVE 270 (320)  60 (14) 102 (24) 19 (22)  5.84 (6.92) 23 POMDO nc — —— — 24 BDVE 351 (418) 233 (23) 376 (47) 53 (35) 10.33 (12.34)

[0279] TABLE 6B VINYL ETHER/DIEPOXIDE/POLYOL PHOTOPOLYMERIZATIONS:SERIES 1B (ERL4206) Enthalpy Induction Time to Conversion Enthalpy No.Vinyl Ether (J/g) Time (sec) Max. (sec) at Max (%) (kcal/mole eq) 17EGDVE 338 213 542 48 5.17 18 DEGDVE 572 76 232 46 10.40 19 TEGDVE 577(478)  66 (16) 144 (42) 26 (17) 11.97 (9.83) 20 HDDVE 492 113 324 358.41 21 CHDMDVE nc — — — — 22 GVE 289 (532)  57 (11) 123 (25) 34 (32) 2.79 (5.14) 23 POMDO nc — — — — 24 BDVE 497 (351) 199 (42) 286 (203) 31(29) 11.11 (7.86)

[0280] TABLE 6C Vinyl Ether/Diepoxide/Polyol Photopolymerizations:series II (Preferred Reactants) Enthalpy Induction Time Time to MaxReactants Ratio Enthalpy (kcal/mol kg.) (sec) (sec) (%) Conv. At Max.Rate Const. No. VE Epoxide V:E w/o ED w/ED w/o ED w/ED w/o ED w/ED w/oED w/ED w/o ED w/ED w/o ED w/ED 25 TEGDVE 6105/pTHF 2:1 360 351 9.569.32 87 18 −249 62 43 38 0.4 2.2 26 1:1 345 353 9.55 9.77 76 16 121 3312 15 0.2 0.9 27 1:2 280 477 8.10 13.80 58 13 104 15 22 18 1.4 10.4 28GVE 6105/pTHF 2:1 170 66 3.13 1.22 75 15 142 38 22 24 0.5 5.3 29 1:1 270320 5.84 6.92 60 14 102 24 19 22 0.7 11.0 30 1:2 147 315 3.67 7.89 12211 396 22 43 21 0.6 8.6 31 BDVE 6105/pTHF 2:1 401 332 11.60 9.60 278 22400 38 28 29 1.7 29.0 32 1:1 351 418 10.33 12.34 233 23 376 47 53 35 2.236.0 33 1:2 198 422 5.96 12.70 163 28 233 42 32 26 3.3 18.6 34 TEGDVE4206/pTHF 2:1 61 507 1.33 11.05 344 22 800 114 62 43 0.2 1.0 35 1:1 577478 11.87 9.83 66 16 144 42 26 17 0.5 0.9 36 1:2 548 400 10.61 7.75 5812 127 15 27 18 1.2 8.3 37 GVE 4206/pTHF 2:1 597 358 8.14 4.88 52 9 11423 25 30 0.9 11.0 38 1:1 289 532 2.79 5.14 57 11 123 25 34 32 1.8 13.739 1:2 467 578 7.14 8.84 59 9 135 13 30 20 0.9 12.0 40 BDVE 4206/pTHF2:1 479 456 11.57 11.02 387 54 479 102 45 26 27.2 2.3 41 1:1 497 35211.11 7.86 199 42 286 203 31 29 1.2 0.6 42 1:2 444 218 9.13 4.48 150 37278 67 24 22 0.8 2.6

[0281] Still further, a substantial amount of vinyl ether is present inmixtures of vinyl ethers, SOCs, epoxides, polyols and the ternaryphotoinitiator system, which form photopolymerizable compositions of thepresent invention. In these mixtures, the vinyl ethers can provide a wayto control the reactivity of the formulation during polymerization. Byusing an epoxide with a vinyl ether, the physical properties of thevinyl ether are improved. This vinyl ether-based composition is furtherimproved by the addition of a polyol which increases the reaction rateof the epoxide. In addition, the low amount of shrinkage and possibleexpansion of SOCs during polymerization further adds benefit to thevinyl ether-based composition. While SOCs tend to retard the reactionrate somewhat, the benefits provided by them outweigh thesedisadvantages for certain applications, especially when an electrondonor is used to promote the reaction. Still further, for a given levelof SOCs, varying the amount of vinyl ether in the composition providesanother way to control the reactivity and resultant physical propertiesof this vinyl ether/SOC/epoxide/polyol mixture. The photopolymerizationof various vinyl ether/epoxide/polyol/SOC compositions is shown by thedata in Tables 7A, 7B, and 7C. The data in these tables shows thatreaction rates increased when an electron donor was used. TABLE 7A VINYLETHER/DIEPOXIDE/POLYOL/TOSU PHOTOPOLYMERIZABLE COMPOSITIONS No DE/pTHFVE VE/EPOXY TOSU Wt. % PI PS ED* 43 UVR6105 TEGDVE 1/1 DEDPM 30 CD1012CQ — 44 UVR6105 TEGDVE 2/1 DEDPM 30 CD1012 CQ — 45 UVR6105 TEGDVE 1/1DEDPM 30 CD1012 CQ X 46 UVR6105 TEGDVE 2/1 DEDPM 30 CD1012 CQ X 47UVR6105 TEGDVE 1/1 DECHE 30 OPIA CQ — 48 UVR6105 TEGDVE 2/1 DECHE 30OPIA CQ — 49 UVR6105 TEGDVE 1/1 DECHE 30 OPIA CQ X 50 UVR6105 TEGDVE 2/1DECHE 30 OPIA CQ X 51 UVR6105 TEGDVE 1/2 DECHE 30 OPIA CQ — 52 UVR6105TEGDVE 1/2 DECHE 30 OPIA CQ X 53 UVR6105 TEGDVE 1/1 DM 30 RHO2074 CQ —54 UVR6105 TEGDVE 1/1 DM 30 RHO2074 CQ X 55 UVR6105 GVE 1/1 DTM 30CD1012 CQ — 56 UVR6105 GVE 1/1 DTM 30 CD1012 CQ X 57 UVR6105 GVE 1/1DEDPM 30 CD1012 CQ —  57A UVR6105 GVE 1/1 DEDPM 30 CD1012 CQ Y 58UVR6105 GVE 1/1 DECHE 30 CD1012 CQ X 59 UVR6105 GVE 1/1 DEDPM 30 RHO2074CQ — 60 UVR6105 GVE 1/1 DEDPM 30 RHO2074 CQ X 61 UVR6105 BDVE 1/1 DTM 30CD1012 CQ — 62 UVR6105 BDVE 1/1 DTM 30 CD1012 CQ X 63 UVR6105 BDVE 1/1DEDPM 30 CD1012 CQ X 64 UVR6105 BDVE 1/1 DECHE 30 CD1012 CQ —  64AUVR6105 BDVE 1/1 DECHE 30 CD1012 CQ Y 65 UVR6105 BDVE 1/1 DTM 30 RHO2074CQ — 66 UVR6105 BDVE 1/1 DTM 30 RHO2074 CQ X 67 ERL4206 TEGDVE 1/1 DTM30 CD1012 CQ — 68 ERL4206 TEGDVE 1/1 DTM 30 CD1012 CQ X 69 ERL4206TEGDVE 1/1 DEDPM 30 CD1012 CQ X 70 ERL4206 TEGDVE 1/1 DECHE 30 CD1012 CQ—  70A ERL4206 TEGDVE 1/1 DECHE 30 CD1012 CQ Y 71 ERL4206 GVE 1/1 DEDPM30 CD1012 CQ — 72 ERL4206 GVE 1/1 DEDPM 30 CD1012 CQ X 73 ERL4206 GVE1/1 DECHE 30 CD1012 CQ — 74 ERL4206 GVE 1/1 DECHE 30 CD1012 CQ X 75ERL4206 BDVE 1/1 DTM 30 CD1012 CQ — 76 ERL4206 BDVE 1/1 DTM 30 CD1012 CQX 77 ERL4206 BDVE 1/1 DEDPM 30 CD1012 CQ — 78 ERL4206 BDVE 1/1 DECHE 30CD1012 CQ X 79 RD2 TEGDVE 1/1 DCHE 5 OPIA CQ — 80 RD2 TEGBVE 1/1 DCHE 5OPIA CQ X

[0282] TABLE 7B VINYL ETHER/DIEPOXIDE/POLYOL/TOSU PHOTOPOLYMERIZATIONRESULTS Rate con No. ΔH_(theory) (J/g) ΔH_(expe)r (J/g) Reacted (%) Ind.Time (sec) Peak Max (sec) ΔH_(exper) at Max (%) (l/min) Comments (20 minirradiation) 43 415 268 65 110 141 10 0.12 44 411 303 74 119 233 34 0.4945 415 303 73 23 44 11 0.32 46 411 325 79 27 49 10 0.95 47 510 264 52127 202 16 0.27 not quite complete 48 507 295 58 135 212 17 0.25 49 510339 66 27 54 13 0.39 50 507 420 83 37 74 11 0.28 51 510 275 54 37 106 190.98 52 510 285 56 24 46 15 1.19 53 435 66 15 219 489 43 0.35 notcomplete 54 435 203 47 20 100 23 0.55 not quite complete 55 672 135 20157 431 40 0.27 not complete 56 672 253 38 27 97 23 0.51 not quitecomplete 57 671 217 32 82 129 16 0.35  57A 671 148 22 92 212 29 0.77 notcomplete 58 764 361 47 20 41 15 1.60 59 672 159 24 26 155 13 0.20 notcomplete 60 672 262 39 26 55 13 0.33 not quite complete 61 392 76 19 164789 53 0.45 not complete 62 392 302 77 96 193 31 1.40 not quite complete63 395 331 84 33 60 26 26.40 64 485 258 53 296 490 33 0.69 not complete 64A 485 276 57 61 138 23 0.69 not quite complete 65 398 153 38 378 80552 0.41 not complete 66 398 308 77 33 143 31 1.40 67 540 240 45 155 28023 0.30 not complete 68 540 317 59 24 59 18 1.04 69 544 484 89 23 52 3159.49 70 635 404 64 105 184 21 0.42 not quite complete  70A 635 277 4452 110 16 0.37 not complete 71 866 413 48 108 161 16 0.50 not quitecomplete 72 866 483 56 22 46 19 2.41 73 968 399 41 101 155 14 0.28 notcomplete 74 968 491 51 32 63 16 0.72 75 498 307 62 279 631 48 0.58 notcomplete 76 498 389 78 29 101 35 1.91 77 504 425 84 205 305 34 7.77 78590 512 87 34 47 19 33.46 79 596 353 59 76 116 24 4.88 80 596 371 62 2247 16 2.43 not quite complete

[0283] TABLE 7C VINYL/ETHER/DIEPOXIDE/POLYOL/TOSU PHOTOPOLYMERIZATEPRODUCTS Wt. Loss No (mg) Description of Post PDSC Product 43 0 Clear,soft, tearable disk 44 0 Clear, rubbery, tearable disk 45 0 Clear, soft,easily punctured and scratched 46 0 Clear, easily punctured 47 0.4Clear, hard, tough solid 48 0 Clear, soft solid, can be scratched andscraped 49 0 Clear, hard, resisted scratching, slightly tacky 50 0Clear, hard, can be punctured and scraped 51 0.2 Clear, hard, indentablesolid 52 1.3 Clear, hard, resisted scratching and puncture 53 0 Partialthink skin on liquid surface 54 0.1 Clear soft gel 55 1.0 Skin on top,liquid beneath surface 56 0.6 Clear, hard, resisted scratching andpuncture 57 0.7 Clear, flexible, tearable disk  57A 0.3 Tacky solid 580.3 Clear, hard, resisted scratching and puncture 59 0.1 Clear,elastomeric, easily torn and punctured 60 0.2 Clear, elastomeric, easilytorn and punctured 61 0.4 Mostly liquid, little evidence of cure 62 0Clear, elastomeric, tacky surface, torn and punctured easily 63 0 Clear,flexible, easily torn and punctured 64 0 Clear, elastomeric, tackysurface, resisted tearing and puncture  64A 0 Elastomeric solid 65 0.3Clear, skin on surface, liquid beneath 66 0 Clear, soft gel 67 0Elastomeric, tacky, easily punctured and torn 68 0.4 Clear, elastomeric,easily punctured and torn 69 0 Light brown hard elastomer, could bescratched and punctured 70 0.9 Very hard, clear, resisted scratching 70A 0 Hard, resisted scratching 71 0.6 Clear, hard, resisted scratchingand puncture 72 0 Clear, hard, tough elastomer, resisted scratching andpuncture 73 — Hard, tacky surface, resisted puncture 74 — — 75 0.1Clear, thin skin, liquid beneath surface 76 0.7 Clear, thick soft skin,liquid beneath surface 77 0.4 Brown, soft gel, liquid at surface 78 0Brown center, amber solid, soft, easily torn and punctured 79 0 Soft,tearable solid 80 0.1 Soft, tearable solid

[0284] The photopolymerizable compositions of the present invention,especially those containing a spiroorthocarbonate, are particularlyuseful as dental restorative materials, with the reaction productforming a matrix in which nonreactive dental fillers may be dispersed.More specifically, a matrix is created from a cationic initiatedreaction product of the various components of the polymerizablecomposition, and a dental filler material is dispersed in the matrix inan amount of between about 10 to 90% by weight based on the total weightof the dental restorative material.

[0285] In dental applications, in general, increasing amounts ofspiroorthocarbonates in the reaction mixture cause decreasing shrinkageof the polymerizable composition. Although vinyl ether is still used ina substantial amount, high loadings of spiroorthocarbonates aredesirable in the reaction mixtures of the present invention that areused as dental composites. When used as dental materials suitable ratiosof the epoxy/hydroxyl-containing material to the SOCs range from 90:10to 40:60 wt % and more preferably from 80:20 to 50:50 wt %. Stillfurther, the present invention provides a system for curingpolymerizable compositions in an acceptable time frame and to sufficientdepth using visible light source equipment already available in dentaloffices. The components of the photopolymerizable composition arepresent in amounts sufficient to provide cure of the composition byexposure to visible light to a cure depth of at least about 1 mm.

[0286] The unique dental restorative materials of the present inventionmay be filled or unfilled and include dental materials such as directaesthetic restorative materials (e.g., anterior and posteriorrestoratives), adhesives and primers for oral hard tissues, sealants,veneers, cavity liners, orthodontic bracket adhesives for use with anytype of bracket (such as metal, plastic and ceramic), crown and bridgecements, prostheses, artificial crowns, artificial teeth, dentures, andthe like. These dental materials are used in the mouth and may bedisposed adjacent to natural teeth. The phrase “disposed adjacent to” asused herein will refer to the placing of a dental material in temporaryor permanent bonded (e.g., adhesive) or touching (e.g., occlusal orproximal) contact with a natural tooth. The term “composite” as usedherein will refer to a filled dental material. The term “adhesive” asused herein will refer to a dental material used for binding twosubstrates. The term “restorative” as used herein will refer to acomposite which is polymerized after it is disposed adjacent to a toothor in direct contact with an adhesive or liner which is adjacent to atooth. The term “prosthesis” as used herein will refer to a compositewhich is shaped and polymerized for its final use (e.g., as crown,bridge, veneer, inlay, onlay or the like) before it is disposed adjacentto a tooth. The term “sealant” as used herein will refer to a lightlyfilled composite or to an unfilled dental material which is cured afterit is disposed adjacent to a tooth. “Polymerizable,” as used herein,refers to curing or hardening the dental material, e.g., byfree-radical, ionic or mixed reaction mechanisms.

[0287] Polymerization of vinyl ether-based reaction mixtures isinitiated by adding suitable amounts of the ternary photoinitiatorsystem and activating the initiator by exposure to a suitable lightsource. As one example, the following elements are combined with thereactants: (a) photoinitiator comprising(4-octyloxyphenyl)phenyl-iodonium hexafluoroantimonate at aconcentration level of 1 wt. percent; (b) the photosensitizer viz.,camphorquinone, concentration level of 0.5 wt. percent; and (c) ethyl4-dimethylaminobenzoate at 0.1 wt. percent. The reactants and thephotoinitiator system components are then mixed by a suitable mixer toform a homogenized mixture. Following mixing, the photopolymerizableformulation is light activated by exposure to a light source such as aXL-3000 dental curing light (3M Co.).

[0288] The photopolymerizable compositions of the present invention haveutility as adhesives, composites and in other applications. Notably, thelack of volume contraction and, in some instances, a slight expansionduring polymerization make the copolymer compositions particularlyuseful in dental applications, such as for dental fillings, precisioncastings, and strain-free composite matrix resins.

[0289] Filler particles can optionally be blended with the alicyclicspiroorthocarbonate and multifunctional copolymer composition to form acomposite resin matrix for dental applications. The filler particles canbe made of any suitable material but typically are inorganic in nature.Among the properties to be considered in selecting a filler are desiredfiller volume level, particle size, particle size distribution, index ofrefraction, radiopacity and hardness. Silicone dioxide is one example ofa suitable filler. The filler particles can be produced by grinding ormilling a material such as quartz or glass to an acceptable size, suchas from 0.02 μm to 100 μm. A range of particles sizes is typically usedto increase the amount of loading of filler material in the resinmatrix. The amount of filler which can be added to the copolymercomposition is dependent upon the total surface area of the fillerparticles. If colloidal size particles in the range of 0.02 to 0.04 μmare used, addition of as little as 5% by weight of the particles will besufficient to modify the viscosity of the copolymer. Desirably, thefiller can be present in an amount of between 20% and 80% by weight.

[0290] In order to increase the strength of the composite, a couplingagent can be used to increase the bonding strength between the fillerparticles and the polymerizable resin. Usually, when a coupling agent isused, it is used to treat the surface of the filler particles. Thisenhanced bonding can improve the physical and mechanical properties ofthe composite and can provide hydrolytic stability by preventing waterfrom penetrating along the interface between the copolymer and thefiller.

[0291] A coupling agent should be chosen which is compatible with thecopolymer and filler and will not significantly contribute to shrinkageof the composite during polymerization. Preferably, the coupling agentdoes not inhibit cationic curing. Organosilanes are generally suitablecoupling agents. Other examples of coupling agents includegamma-methacryloxypropyltrimethoxysilane,beta-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane,gamma-glycidoxypropyltri-methoxysilane, and the like. Preferably,3-glycidoxypropyltrimethoxysilane is used as a coupling agent whensilicone dioxide is used as the filler material.

[0292] The photopolymerizable compositions of the invention aresensitive throughout the visible spectral region, and can photocurerapidly in the absence of heat, and in fact, they can cure at or belowbody temperature, to polymers having desirable properties. For purposesof the present invention, visible light is defined as light having awavelength of between about 400 and 700 nanometers. Thephotopolymerization of the compositions of the invention occurs onexposure of the compositions to any source of radiation emitting actinicradiation within the visible spectral region at the wavelength ofabsorption of the photosensitizer. Exposures may be from less than about1 second to 10 minutes or more, depending upon the amounts andparticular components of the compositions utilized and depending uponthe radiation source and distance from the source and the thickness ofthe composition to be cured. The compositions of the invention aretypically one-part, stable compositions having very good shelf life andgood thermal stability.

[0293] Still further, the polymerizable compositions of the presentinvention are capable of rapidly undergoing photoinitiatedpolymerization with less volume shrinkage and yielding polymers withless stress than conventional compositions so that they are moredesirable for use as dental materials, such as for sealing cracks andfixtures in tooth structures and tooth restoratives. These compositionspossess the mechanical and physical properties necessary for use as acomposite material, including as a dental material matrix. In addition,these polymerizable compositions are capable of forming chemical bondswith substrates in a multifunctional group for use as an adhesive. Thisadhesive can be a cationically photoinitiated adhesive that iscompatible with a cationically photoinitiated dental material system soas to obtain reduced shrinkage and enhanced bond strength when adhesivebonding low stress dental restorative materials to dentin and enamelsubstrates. In addition, these compositions can be cationicallyphotopolymerized by visible light irradiation.

[0294] In certain applications, the use of a filler may be appropriate.The choice of filler affects important properties of the composite suchas its appearance, radiopacity and physical and mechanical properties.Appearance is affected in part by adjustment of the amounts and relativerefractive indices of the ingredients of the composite, thereby allowingalteration of the translucence, opacity or pearlescence of thecomposite. Vinyl ether compositions of the invention, either alone or inadmixture with diluent monomer, can be prepared with refractive indiceswhich approach or approximate the refractive indices of fillers such asquartz (refractive index 1.55), submicron silica (1.46), and 5.5:1 moleratio SiO₂:ZrO₂ non-vitreous microparticles (1.54). In this way theappearance of the dental material can, if desired, be made to closelyapproximate the appearance of natural dentition.

[0295] Radiopacity is a measurement of the ability of the composite tobe detected by x-ray examination. Frequently a radiopaque composite willbe desirable, for instance, to enable the dentist to determine whetheror not a filling remains sound. Under other circumstances anon-radiopaque composite may be desirable.

[0296] The amount of filler which is incorporated into the composite(referred to herein as the “loading level” and expressed as a weightpercent based on the total weight of the dental material) will varydepending on the type of filler, the vinyl ether resin and othercomponents of the composition, and the end use of the composite.

[0297] For certain dental material applications (e.g., adhesives,composites, and sealants), the monomeric compositions of the inventioncan be lightly filled (e.g., having a loading level of less than about40 weight percent) or unfilled. Preferably, the viscosity of the dentalmaterial is sufficiently low to allow its penetration into pits andfissures of occlusal tooth surfaces as well as into etched areas ofenamel, thereby aiding in the retention of the dental material. Inapplications where high strength or durability are desired (e.g.,anterior or posterior restoratives, prostheses, crown and bridgecements, artificial crowns, artificial teeth and dentures) the loadinglevel can be as high as about 95 weight percent. For most dentalrestorative and prosthetic applications a loading level of between about70 and 90 weight percent is generally preferred.

[0298] Fillers may be selected from one or more of any material suitablefor incorporation in compositions used for medical applications, such asfillers currently used in dental restorative compositions and the like.The filler is finely divided and preferably has a maximum particlediameter less than about 50 micrometers and an average particle diameterless than about 10 micrometers. The filler can have a unimodal orpolymodal (e.g., bimodal) particle size distribution. The filler can bean inorganic material. It can also be a crosslinked organic materialthat is insoluble in the polymerizable resin, and is optionally filledwith inorganic filler. The filler should in any event be non-toxic andsuitable for use in the mouth. The filler can be radiopaque, radiolucentor non-radiopaque. Still further, the filler should not inhibit thecationic curing of the polymerizable composition.

[0299] Examples of suitable inorganic fillers are naturally-occurring orsynthetic materials such as quartz, nitrides (e.g., silicon nitride),glasses derived from, for example, Ce, Sb, Sn, Zr, Sr, Ba and Al,colloidal silica, feldspar, borosilicate glass, kaolin, talc, titania,and zinc glass; low Mohs hardness fillers such as those described inU.S. Pat. No. 4,695,251; and submicron silica particles (e.g., pyrogenicsilicas such as the “Aerosil” Series “OX 50,” “130,” “150” and “200”silicas sold by Degussa dn “Cab-O-Sil M5” silica sold by Cabot Corp.).Examples of suitable organic filler particles include filled or unfilledpulverized polycarbonates, polyepoxides, and the like. Preferred fillerparticles are quartz, submicron silica, and non-vitreous microparticlesof the type described in U.S. Pat. No. 4,503,169. Metallic fillers mayalso be incorporated, such as particulate metal filler made from a puremetal such as those of Groups IVA, VA, VIA, VIIA, VIII, IB, or IIB,aluminum, indium, and thallium of Group IIIB, and tin and lead of GroupIVB, or alloys thereof. Conventional dental amalgam alloy powders,typically mixtures of silver, tin, copper, and zinc, may also optionallybe incorporated. The particulate metallic filler preferably has anaverage particle size of about 1 micron to about 100 microns, morepreferably 1 micron to about 50 microns. Mixtures of these fillers arealso contemplated, as well as combination fillers made from organic andinorganic materials.

[0300] The dental materials of the present invention can also containsuitable adjuvants such as accelerators, inhibitors, absorbers,stabilizers, pigments, dyes, viscosity modifiers, surface tensiondepressants and wetting aids, antioxidants, fluoride release agents, andother ingredients well known to those skilled in the art.

[0301] The amounts and types of each ingredient in the dental materialshould be adjusted to provide the desired physical and handlingproperties before and after cure. For example, the cure rate, curestability, fluidity, compressive strength, tensile strength anddurability of the dental material typically are adjusted in part byaltering the types and amounts of polymerization initiator(s) and, ifpresent, the loading and particle size distribution of filler(s). Suchadjustments typically are carried out empirically based on experiencewith dental materials of the prior art.

[0302] When the dental material is applied to a tooth, the tooth canoptionally be pre-treated with a primer such as dentin or enameladhesive by methods known to those skilled in the art.

[0303] From the foregoing, it will be seen that this invention is onewell adapted to attain all the ends and objects hereinabove set forthtogether with other advantages that are obvious and inherent to thestructure. It will be understood that certain features andsubcombinations are of utility and may be employed without reference toother features and subcombinations. This is contemplated by and iswithin the scope of the claims. Since many possible embodiments may bemade of the invention without departing from the scope thereof, it is tobe understood that all matter herein set forth is to be interpreted asillustrative and not in a limiting sense.

Having thus described the invention, what is claimed is:
 1. Aphotopolymerizable composition, comprising a mixture of: (a) asubstantial amount of vinyl ether; and (b) a photoinitiator systemcomprising: (i) an iodonium salt; (ii) a visible light sensitizer; and(iii) an electron donor compound, wherein the photoinitiator system hasa photoinduced potential greater than or equal to that ofN,N-dimethylaniline in a standard solution of 2.9×10⁻⁵ moles/g diphenyliodonium hexafluoroantimonate and 1.5×10⁻⁵ moles/g camphorquinone in2-butanone.
 2. The photopolymerizable composition of claim 1, whereinthe components of said composition are present in amounts sufficient toprovide cure of said photopolymerizable composition by exposure tovisible light to a cure depth of at least about 1 mm.
 3. Thephotopolymerizable composition of claim 1, wherein said vinyl ether isselected from the group consisting of tri(ethylene glycol) divinyl ether(TEGDVE), glycidyl vinyl ether (GVE), butanediol vinyl ether (BDVE),di(ethylene glycol) divinyl ether (DEGDVE), 1,4-cyclohexanedimethanoldivinyl ether (CHDMDVE), 4-(1-propenyloxymethyl)-1,3-dioxolan-2-onePOMDO), 2-chloroethyl vinyl ether (CEVE), or 2-ethylhexyl vinyl ether(EHVE), ethyl vinyl ether (EVE), n-propyl vinyl ether (NPVE), isopropylvinyl ether (IPVE), n-butyl vinyl ether (NBVE), isobutyl vinyl ether(IBVE), octadecyl vinyl ether (ODVE), cyclohexyl vinyl ether (CVE),butanediol divinyl ether (BDDVE), hydroxybutyl vinyl ether (HBVE),cyclohexanedimethanol monovinyl ether (CHMVE), tert-butyl vinyl ether(TBVE), tert-amyl vinyl ether (TAVE), dodecyl vinyl ether (DDVE),ethyleneglycol divinyl ether (EGDVE), ethyleneglycol monovinyl ether(EGMVE), hexanediol divinyl ether (HDDVE), hexanediol monovinyl ether(HDMVE), diethyleneglycol monovinyl ether (MVE-2), triethyleneglycolmethyl vinyl ether (MTGVE), tetraethyleneglycol divinyl ether (DVE-4),trimethylolpropane trivinyl ether (TMPTVE), aminopropyl vinyl ether(APVE), poly-tetrahydrofuran divinyl ether (PTHFDVE), pluriol-E200divinyl ether (PEG200-DVE), n-butyl vinyl ether (n-BVE),4-hydroxybutylvinylether (HBVE), ethylene glycol butyl vinyl ether(EGBVE), 2-diethylaminoethyl vinyl ether (DEAEVE), dipropropylene glycoldivinyl ether (DPGDVE), octadecylvinylether (ODVE), a vinyl etherterminated aromatic ester monomer, a vinyl ether terminated aliphaticester monomer, a vinyl ether terminated aliphatic urethane oligomer, anda vinyl ether terminated aromatic urethane oligomer.
 4. Thephotopolymerizable composition of claim 1, further comprising: acompound of the formula:

wherein R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl or substitutedaryl, or R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6;—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2; and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, and R₆ and R₇, provided that R₃, R₄, R₇, and R₈ are hydrogen whenR₁•R₂ and R₅•R₆ are independently selected from the group consisting of—CH₂(CH₂)_(n)CH₂— where n=3, 4, 5 and 6 so as to form an alicyclic ringbetween R₁ and R₂ and between R₅ and R₆; R₂, R₃, R₄, R₆, R₇, and R₈ arehydrogen when R₁ and R₅ are independently selected from the groupconsisting of alkyl, aryl, substituted alkyl, and substituted aryl; R₁,R₄, R₅, and R₈ are hydrogen when R₂ and R₆ are independently selectedfrom the group consisting of alkyl, aryl, substituted alkyl, andsubstituted aryl and R₃ and R₇ are independently selected from the groupconsisting of —(CH₂)_(n)—O—(O═C)—R₉ where n=1 and 2 and R₉=H, alkyl,aryl, substituted alkyl or substituted aryl; R₁, R₄, R₅, and R₈ arehydrogen when R₂ and R₃ are independently selected from the groupconsisting of H, alkyl, aryl, substituted alkyl, and substituted aryland R₆•R₇=—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form analicyclic ring between R₆and R₇; R₁, R₄, R₅, and R₈ are hydrogen whenR₂•R₃ and R₆•R₇ are independently selected from the group consisting of—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form an alicyclicring between R₂ and R₃ and between R₆ and R₇; R₁, R₄, R₅, and R₈ arehydrogen when R₂ is independently selected from the group consisting of6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆, and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl; R₁, R₄, R₅, and R₈ arehydrogen when R₂ and R₃ are independently selected from the groupconsisting of 6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl; R₃, R₄, R₅, R₆, R₇, and R₈ areindependently selected from the group consisting of the group consistingof hydrogen, alkyl, aryl, substituted alkyl, and substituted aryl, whenR₁•R₂=—O— so as to form an oxirane ring between R₁ and R₂; and R₃, R₄,R₇, and R₈ are independently selected from the group consisting ofhydrogen, alkyl, aryl, substituted alkyl, and substituted aryl, whenR₁•R₂ and R₅•R₆=—O— so as to form an oxirane ring between R₁ and R₂ andbetween R₅ and R₆.
 5. The photopolymerizable composition of claim 1,further comprising: an epoxide.
 6. The photopolymerizable composition ofclaim 5, wherein said epoxide is selected from the group consisting ofoctadecylene oxide; epichlorohydrin; styrene oxide; vinyl cyclohexeneoxide; glycidol; glycidylmethacrylate; diglycidyl ether of Bisphenol A;vinylcyclohexene dioxide; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate;3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexenecarboxylate; bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate;bis(2,3-epoxycyclopentyl) ether; aliphatic epoxy modified frompolypropylene glycol; dipentene dioxide; epoxidized polybutadiene;silicone resin containing epoxy functionality; halogenated epoxy resins;1,4-butanediol diglycidyl ether of phenolformaldehyde novolak;resorcinol diglycidyl ether; bis(3,4-epoxycyclohexyl)adipate;2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-meta-dioxane;vinylcyclohexene monoxide 1,2-epoxyhexadecane; alkyl glycidyl etherssuch as alkyl C₈-C₁₀ glycidyl ether; alkyl C₁₂-C₁₄ glycidyl ether; butylglycidyl ether; cresyl glycidyl ether; p-ter butylphenyl glycidyl ether;polyfunctional glycidyl ethers such as diglycidyl ether of1,4-butanediol; diglycidyl ether of neopentyl glycol; diglycidyl etherof cyclohexanedimethanol; trimethylol ethane triglycidyl ether;trimethylol propane triglycidyl ether; polyglycidyl ether of analiphatic polyol; polyglycol diepoxide; bisphenol F epoxides;9,9-bis[4-(2,3-epoxypropoxy)-phenyl]fluorenone; epichlorohydrins;alkylene oxides; and alkenyl oxides.
 7. The photopolymerizablecomposition of claim 5, further comprising: a polyol.
 8. Thephotopolymerizable composition of claim 7, wherein said polyol isselected from the group consisting of alkanols, monoalkyl ethers ofpolyoxyalkyleneglycols, monoalkyl ethers of alkylene-glycols, alkyleneglycols, polyhydroxyalkanes, N,N-bis(hydroxyethyl)benzamide,2-butyne-1,4-diol, 4,4-bis(hydroxymethyl)diphenylsulfone, castor oil,polyoxyethylene glycols, polyoxypropylene glycols, polytetramethyleneether glycols, polyvinylacetal resins containing pendent hydroxylgroups, modified cellulose polymers, hydroxy-terminated polyesters;hydroxy-terminated polylactones, polycaprolactones; fluorinatedpolyoxyethylene glycols, fluorinated polyoxypropylene glycols,hydroxy-terminated polyalkadienes, and 2-oxepanone polymer with2-ethyl-2-(hydroxymethyl)-1,3-propane diol.
 9. The photopolymerizablecomposition of claim 4, further comprising: an epoxide.
 10. Thephotopolymerizable composition of claim 9, wherein said epoxide isselected from the group consisting of octadecylene oxide;epichlorohydrin; styrene oxide; vinyl cyclohexene oxide; glycidol;glycidylmethacrylate; diglycidyl ether of Bisphenol A; vinylcyclohexenedioxide; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate;3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexenecarboxylate; bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate;bis(2,3-epoxycyclopentyl) ether; aliphatic epoxy modified frompolypropylene glycol; dipentene dioxide; epoxidized polybutadiene;silicone resin containing epoxy functionality; flame retardant epoxyresins; 1,4-butanediol diglycidyl ether of phenolformaldehyde novolak;resorcinol diglycidyl ether; bis(3,4-epoxycyclohexyl)adipate;2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-meta-dioxane;vinylcyclohexene monoxide 1,2-epoxyhexadecane; alkyl glycidyl etherssuch as alkyl C₈-C₁₀ glycidyl ether; alkyl C₁₂-C₁₄ glycidyl ether; butylglycidyl ether; cresyl glycidyl ether; p-ter butylphenyl glycidyl ether;polyfunctional glycidyl ethers such as diglycidyl ether of1,4-butanediol; diglycidyl ether of neopentyl glycol; diglycidyl etherof cyclohexanedimethanol; trimethylol ethane triglycidyl ether;trimethylol propane triglycidyl ether; polyglycidyl ether of analiphatic polyol; polyglycol diepoxide; bisphenol F epoxides;9,9-bis[4-(2,3-epoxypropoxy)-phenyl]fluorenone; epichlorohydrins;alkylene oxides; and alkenyl oxides.
 11. The photopolymerizablecomposition of claim 9, further comprising: a polyol.
 12. Thephotopolymerizable composition of claim 11, wherein said polyol isselected from the group consisting of alkanols, monoalkyl ethers ofpolyoxyalkyleneglycols, monoalkyl ethers of alkylene-glycols, alkyleneglycols, polyhydroxyalkanes, N,N-bis(hydroxyethyl)benzamide,2-butyne-1,4-diol, 4,4-bis(hydroxymethyl)diphenylsulfone, castor oil,polyoxyethylene glycols, polyoxypropylene glycols, polytetramethyleneether glycols, polyvinylacetal resins containing pendent hydroxylgroups, modified cellulose polymers, hydroxy-terminated polyesters;hydroxy-terminated polylactones, polycaprolactones; fluorinatedpolyoxyethylene glycols, fluorinated polyoxypropylene glycols,hydroxy-terminated polyalkadienes, and 2-oxepanone polymer with2-ethyl-2-(hydroxymethyl)-1,3-propane diol.
 13. The photopolymerizablecomposition of claim 1, wherein said electron donor compound has thefollowing structural formula:

wherein each R₁ is independently H; C₁₋₁₈ alkyl; C₁₋₁₈ alkyl having atleast one substituent selected from the group consisting of a halogen,—CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈ cycloalkyl, aryl,COOH, COOC₁₋₁₈ alkyl, (C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, SO₃R², aryl, andaryl having at least one electron withdrawing group as a substituent; orthe R¹ groups together form a ring; where R² is H; C₁₋₁₈ alkyl; or C₁₋₁₈alkyl having at least one substituent selected from the group consistingof a halogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈cycloalkyl, aryl, COOH, COOC₁₋₁₈ alkyl, (C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl,and SO₃H; and Ar is aryl or aryl having at least one electronwithdrawing group as a substituent.
 14. The photopolymerizablecomposition of claim 13, wherein said aryl substituent on said electrondonor compound includes at least one electron withdrawing group selectedfrom the group consisting of —COOH, —COOR², —SO₃R², —CN, —CO—C₁₋₁₈alkyl, and C(O)H groups.
 15. The photopolymerizable composition of claim1, wherein said electron donor compound has the following structuralformula:

wherein n=1-3; each R₃ is independently H, C₁₋₁₈ alkyl, or C₁₋₁₈ alkylhaving at least one substituent selected from the group consisting of ahalogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈ cycloalkyl,aryl, substituted aryl, —COOH, —COOC₁₋₁₈ alkyl, —(C₁₋₁₈ alkyl)₀₋₁—COH,—(C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, —CO—C₁₋₁₈ alkyl, —C(O)H and —C₂₋₁₈alkenyl groups; and each R₄ is independently C₁₋₁₈ alkyl or C₁₋₁₈ alkylhaving at least one substituent selected from the group consisting of ahalogen, —CN, —OH, —SH, C₁₋₁₈ alkoxy, C₁₋₁₈ alkylthio, C₃₋₁₈ cycloalkyl,aryl, substituted aryl, —COOH, —COOC₁₋₁₈ alkyl, —(C₁₋₁₈ alkyl)₀₋₁—COH,—(C₁₋₁₈ alkyl)₀₋₁—CO—C₁₋₁₈ alkyl, —CO—C₁₋₁₈ alkyl, —C(O)H and —C₂₋₁₈alkenyl groups.
 16. The photopolymerizable composition of claim 1,wherein said electron donor compound is selected from the groupconsisting of 4,4′-bis(diethylamino)benzophenone, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylamino benzoicacid, 4-dimethylaminobenzoin, 4-dimethylaminobenzaldehyde,4-dimethylaminobenzonitrile, 1,2,4-trimethoxybenzene, andN-phenylglycine.
 17. The photopolymerizable composition of claim 1,wherein said iodonium salt is selected from the group consisting ofdiphenyliodonium tetrafluoroborate; di(4-methylphenyl)iodoniumtetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate;di(4-heptylphenyl)iodonium tetrafluoroborate; di(3-nitrophenyl)iodoniumhexafluorophosphate; di(4-chlorophenyl)iodonium hexafluorophosphate;di(naphthyl)iodonium tetrafluoroborate;di(4-trifluoromethylphenyl)iodonium tetrafluoroborate; diphenyliodoniumhexafluorophosphate; di(4-methylphenyl)iodonium hexafluorophosphate;diphenyliodonium hexafluoroarsenate; di(4-phenoxyphenyl)iodoniumtetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate;3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate;diphenyliodonium hexafluoroantimonate; 2,2′-diphenyliodoniumtetrafluoroborate; di(2,4-dichlorophenyl)iodonium hexafluorophosphate;di(4-bromophenyl)iodonium hexafluorophosphate; di(4-methoxyphenyl)iodonium hexafluorophosphate; di(3-carboxyphenyl)iodoniumhexafluorophosphate; di(3-methoxycarbonylphenyl)iodoniumhexafluorophosphate; di(3-methoxysulfonylphenyl)iodoniumhexafluorophosphate; di(4-acetamidophenyl)iodonium hexafluorophosphate;di(2-benzothienyl) iodonium hexafluorophosphate; (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate; diphenyliodoniumhexafluoroantimonate; [4-(2-hydroxytetradecyloxyphenyl)]phenyliodoniumhexafluoroantimonate; and [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium tetrakis (pentafluorophenyl)borate.
 18. Thephotopolymerizable composition of claim 17, wherein said visible lightsensitizer is selected from the group consisting of camphorquinone;2-chlorothioxanthan-9-one; glyoxal; biacetyl;3,3,6,6-tetramethylcyclohexanedione;3,3,7,7-tetramethyl-1,2-cycloheptanedione;3,3,8,8-tetramethyl-1,2-cyclooctanedione;3,3,18,18-tetramethyl-1,2-cyclooctadecanedione; dipivaloyl; benzyl;furyl; hydroxybenzyl; 2,3-butanedione; 2,3-pentanedione;2,3-hexanedione; 3,4-hexanedione; 2,3-heptanedione; 3,4-heptanedione;2,3-octanedione; 4,5-octanedione; and 1,2-cyclohexanedione.
 19. Thephotopolymerizable composition of claim 1, wherein said composition is acomponent in a formulation for use in an application selected from thegroup consisting of graphic arts imaging, printing plates, photoresists,solder masks, electronic conformal coatings, coated abrasives, magneticmedia, photocurable adhesives, and photocurable composites.
 20. A dentalrestorative material, comprising: (A) a matrix comprising a resincomprised of: (a) a vinyl ether; and (b) a photoinitiator systemcomprising: (i) an iodonium salt; (ii) a visible light sensitizer; and(iii) an electron donor compound, wherein the photoinitiator system hasa photoinduced potential greater than or equal to that ofN,N-dimethylaniline in a standard solution of 2.9×10⁻⁵ moles/g diphenyliodonium hexafluoroantimonate and 1.5×10⁻⁵ moles/g camphorquinone in2-butanone; and (B) a dental filler dispersed in said matrix in anamount of between about 10 to 90% by weight based on the total weight ofthe dental restorative material.
 21. The dental restorative material ofclaim 20, wherein said dental material is an adhesive.
 22. The dentalrestorative material of claim 20, wherein said dental material is acomposite.
 23. The dental restorative material of claim 20, wherein saidmatrix is further comprised of a spiroorthocarbonate compound of theformula:

wherein R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl or substitutedaryl, or R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6;—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2; and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, and R₆ and R₇; provided that R₃, R₄, R₇, and R₈ are hydrogen whenR₁•R₂ and R₅•R₆ are independently selected from the group consisting of—CH₂(CH₂)_(n)CH₂— where n=3, 4, 5 and 6 so as to form an alicyclic ringbetween R₁ and R₂ and between R₅ and R₆; R₂, R₃, R₄, R₆, R₇, and R₈ arehydrogen when R₁ and R₅ are independently selected from the groupconsisting of alkyl, aryl, substituted alkyl, and substituted aryl; R₁,R₄, R₅, and R₈ are hydrogen when R₂ and R₆ are independently selectedfrom the group consisting of alkyl, aryl, substituted alkyl, andsubstituted aryl and R₃ and R₇ are independently selected from the groupconsisting of —(CH₂)_(n)—O—(O═C)—R₉ where n=1 and 2 and R₉=H, alkyl,aryl, substituted alkyl or substituted aryl; R₁, R₄, R₅, and R₈ arehydrogen when R₂ and R₃ are independently selected from the groupconsisting of H, alkyl, aryl, substituted alkyl, and substituted aryland R₆•R₇=—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form analicyclic ring between R₆ and R₇; R₁, R₄, R₅, and R₈ are hydrogen whenR₂•R₃ and R₆•R₇ are independently selected from the group consisting of—CH₂-epoxy-(CH₂)_(n)—CH₂— where n=0, 1, and 2 so as to form an alicyclicring between R₂ and R₃ and between R₆ and R₇; R₁, R₄, R₅, and R₈ arehydrogen when R₂ is independently selected from the group consisting of6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆. and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl; R₁, R₄, R₅, and R₈ arehydrogen when R₂ and R₃ are independently selected from the groupconsisting of 6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy, and(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl; R₃, R₄, R₅, R₆, R₇, and R₈ areindependently selected from the group consisting of the group consistingof hydrogen, alkyl, aryl, substituted alkyl, and substituted aryl, whenR₁•R₂=—O— so as to form an oxirane ring between R₁ and R₂; and R₃, R₄,R₇, and R₉ are independently selected from the group consisting ofhydrogen, alkyl, aryl, substituted alkyl, and substituted aryl, whenR₁•R₂ and R₅•R₆=—O— so as to form an oxirane ring between R₁ and R₂ andbetween R₅ and R₆.
 24. The dental restorative material of claim 20,wherein said matrix is further comprised of an epoxide.
 25. The dentalrestorative material of claim 24, wherein said matrix is furthercomprised of a polyol.
 26. The dental restorative material of claim 23,wherein said matrix is further comprised of an epoxide.
 27. The dentalrestorative material of claim 26, wherein said matrix is furthercomprised of a polyol.
 28. A compound of the formula:

wherein R₁-R₈ are independently selected from the group consisting ofhydrogen; alkyl; aryl; substituted alkyl; substituted aryl;6-oxabicyclo[3.1.0]hex-2-yl; 6-oxabicyclo[3.1.0]hex-3-yl;(6-oxabicyclo[3.1.0]hex-2-yl)methyl;(6-oxabicyclo[3.1.0]hex-3-yl)methyl;(6-oxabicyclo[3.1.0]hex-2-yl)methoxy;(6-oxabicyclo[3.1.0]hex-3-yl)methoxy; 7-oxabicyclo[4.1.0]hept-2-yl;7-oxabicyclo[4.1.0]hept-3-yl; (7-oxabicyclo[4.1.0]hept-2-yl)methyl;(7-oxabicyclo[4.1.0]hept-3-yl)methyl;(7-oxabicyclo[4.1.0]hept-2-yl)methoxy;(7-oxabicyclo[4.1.0]hept-3-yl)methoxy; and —(CH₂)_(n)—O—(O═C)—R₉, wheren=1 through 9 and R₉=H, alkyl, aryl, substituted alkyl and substitutedaryl, or R₁•R₂, R₂•R₃, R₅•R₆, and R₆•R₇ are independently selected fromthe group consisting of —CH₂(CH₂)_(n)CH₂— where n=3, 4, 5, and 6 and—CH₂-epoxy-(CH₂)_(n—CH) ₂— where n=0, 1, and 2, and —O— so as to form analicyclic ring or an oxirane ring between R₁ and R₂, R₂ and R₃, R₅ andR₆, or R₆ and R₇; provided that R₁, R₄, R₅, and R₈ are hydrogen when R₂is independently selected from the group consisting of6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy,(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃, R₆, and R₇ areindependently selected from the group consisting of hydrogen, alkyl,aryl, substituted alkyl, and substituted aryl; R₁, R₄, R₅, and R₈ arehydrogen when R₂ and R₃ are independently selected from the groupconsisting of 6-oxabicyclo[3.1.0]hex-2-yl, 6-oxabicyclo[3.1.0]hex-3-yl,(6-oxabicyclo[3.1.0]hex-2-yl)methyl,(6-oxabicyclo[3.1.0]hex-3-yl)methyl,(6-oxabicyclo[3.1.0]hex-2-yl)methoxy,(6-oxabicyclo[3.1.0]hex-3-yl)methoxy, 7-oxabicyclo[4.1.0]hept-2-yl,7-oxabicyclo[4.1.0]hept-3-yl, (7-oxabicyclo[4.1.0]hept-2-yl)methyl,(7-oxabicyclo[4.1.0]hept-3-yl)methyl,(7-oxabicyclo[4.1.0]hept-2-yl)methoxy,(7-oxabicyclo[4.1.0]hept-3-yl)methoxy, and R₃ and R₇ are independentlyselected from the group consisting of hydrogen, alkyl, aryl, substitutedalkyl, and substituted aryl; R₃, R₄, R₅, R₆, R₇, and R₈ areindependently selected from the group consisting of the group consistingof hydrogen, alkyl, aryl, substituted alkyl, and substituted aryl, whenR₁•R₂ =—O— so as to form an oxirane ring between R₁ and R₂; R₃, R₄, R₇,and R₈ are independently selected from the group consisting of the groupconsisting of hydrogen, alkyl, aryl, substituted alkyl, and substitutedaryl, when R₁•R₂ and R₅•R₆=—O— so as to form an oxirane ring between R₁and R₂ and between R₅ and R₆; R₁, R₄, R₅, and R₈ are hydrogen when R₂and R₃ are ethyl and R₆•R₇ are —CH₂-epoxy-(CH₂)_(n)—CH₂— where n=1 and 2so as to form an alicyclic ring between R₆and R₇; and R₁, R₄, R₅, and R₈are hydrogen when R₂•R₃ and R₆•R₇ are —CH₂-epoxy-(CH₂)_(n)—CH₂— wheren=1 and 2 so as to form an alicyclic ring between R₂ and R₃ and R₆ andR₇.
 29. The compound of claim 28, wherein said compound is selected fromthe group consisting of5,5-diethyl-19-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′4″-bicyclo[4.1.0]heptane],7,26-dioxatrispiro[bicyclo[4.1.0]heptane-4,5′-1,3-dioxane-2′2″-1,3-dioxane-5″,4″-bicyclo[4.1.0]heptane],5-5-diethyl-18-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′3″-bicyclo[3.1.0]hexane],and6,24-dioxatrispiro[bicyclo[3.1.0]hexane-3,5′-1,3-dioxane-2′2″-1,3-dioxane-5″3′″-bicyclo[3.1.0]hexane],3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-3-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methoxy]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-3-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]spiro[5.5]undecane,3,9-bis[(6-oxabicyclo[3.1.0]hex-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-3-yl)methyl]spiro[5.5]undecane,3,9-bis(7-oxabicyclo[4.1.0]hept-3-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[4.1.0]hept-2-yl)methyl]spiro[5.5]undecane,3,9-bis(7-oxabicyclo[4.1.0]hept-2-yl)methyl]-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis(6-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(6-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane,3,9-bis(6-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,9-bis(7-oxabicyclo[3.1.0]hex-3-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[3.1.0]hex-3-yl)spiro[5.5]undecane,3,9-bis(7-oxabicyclo[3.1.0]hex-2-yl)-3-ethyl-1,5,7,11-tetraoxaspiro[5.5]undecane,3,3-diethyl-1,5,7,11-tetraoxa-9-(7-oxabicyclo[3.1.0]hex-2-yl)spiro[5.5]undecane,2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],5,12-dimethyl-2,4,7,9,11,14-hexaoxaspiro[bicyclo[4.1.0]heptane-3,3′bicyclo[4.1.0]heptane],4,5,5,11-tetramethyl-8,10-13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane],and5,5-dimethyl-8,10,13-trioxaspiro[1,3-dioxane-2,3′-bicyclo[4.1.0]heptane].